Cyclic compound, method for producing the same, radiation-sensitive composition, and resist pattern formation method

ABSTRACT

A cyclic compound of the present invention has a molecular weight of 500 to 5000, and is represented by the following formula (1):

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a U.S. National Stage Application filed under 35U.S.C. §371 of International Application PCT/JP 2012/079528, filed Nov.14, 2012, designating the United States, which claims priority fromJapanese Patent Application 2011-253312, filed Nov. 18, 2011, thecomplete disclosures of which are hereby incorporated herein byreference in their entirety for all purposes.

TECHNICAL FIELD

The present invention relates to a cyclic compound represented by aspecific chemical constitution formula, a radiation-sensitivecomposition containing the same, and a resist pattern formation methodusing the composition.

BACKGROUND ART

Conventional typical resist materials are polymeric resist materialscapable of forming amorphous thin films. Examples thereof include apolymeric resist material such as polymethyl methacrylate, polyhydroxystyrene with an acid dissociation reactive group, or polyalkylmethacrylate. A line pattern of about 45 to 100 nm is formed byirradiating a resist thin film made by coating a substrate with asolution of such a polymer resist material with ultraviolet, farultraviolet, electron beam, extreme ultraviolet (EUV), and X-ray or thelike.

However, because polymeric resist materials have a molecular weight aslarge as about 10,000 to 100,000 and also wide molecular weightdistribution, in lithography using a polymeric resist material,roughness occurs on a fine pattern surface; the pattern dimensionbecomes difficult to be controlled; and the yield decreases. Therefore,there is a limitation in miniaturization with lithography using aconventional polymeric resist material. In order to make a finerpattern, various low molecular weight resist materials have beenproposed.

For example, an alkaline development type negative typeradiation-sensitive composition (For example, see Patent Documents 1 and2) using a low molecular weight polynuclear polyphenolic compound as amain component has been suggested.

As a low molecular weight resist material candidate, an alkalinedevelopment type negative type radiation-sensitive composition using alow molecular weight cyclic polyphenolic compound (For example, seePatent Documents 3 and 4, and Non Patent Document 1) as a main componenthas been suggested.

LIST OF PRIOR ART DOCUMENTS Patent Document

-   Patent Document 1: Japanese Patent Application Laid-Open No.    2005-326838-   Patent Document 2: Japanese Patent Application Laid-Open No.    2008-145539-   Patent Document 3: Japanese Patent Application Laid-Open No.    2009-173623-   Patent Document 4: International Publication No. WO 2011/024916

Non Patent Document

-   Non Patent Document 1: T. Nakayama, M. Nomura, K. Haga, M. Ueda:    Bull. Chem. Soc. Jpn., 71, 2979 (1998)

SUMMARY OF INVENTION Problems to be Solved by Invention

However, alkaline development type negative type radiation-sensitivecompositions described in Patent Documents 1 and 2 have insufficientheat resistance and may disable the formation of a resist pattern havinga good shape.

In alkaline development type negative type radiation-sensitivecompositions described in Patent Documents 3 and 4 and Non PatentDocument 1, a low molecular weight cyclic polyphenol compound isexpected to provide a resist pattern with small molecular size, highresolution and small roughness due to its low molecular weight. Also,the low molecular weight cyclic polyphenol compound provides high heatresistance even with the low molecular weight, by having a rigid cyclicstructure in its backbone. However, the currently known low molecularweight cyclic polyphenol compound has low solubility in a safe solventused for a semiconductor production process. Therefore, theradiation-sensitive composition containing a low molecular weight cyclicpolyphenol compound and a safe solvent has low sensitivity, which maydisable the formation of a resist pattern having a good shape. In orderto form a resist pattern having high sensitivity and a good shape, animprovement in the low molecular weight cyclic polyphenol compound hasbeen desired.

Then, the object of the present invention is to provide a cycliccompound capable of forming a radiation-sensitive composition which hashigh solubility in a safe solvent, has high sensitivity, and provides agood resist pattern shape having small roughness, a method for producingthe cyclic compound, a radiation-sensitive composition containing thecyclic compound, and a resist pattern formation method using theradiation-sensitive composition.

Means for Solving Problems

The inventors have, as a result of devoted examinations to solve theabove problems, found out that a cyclic compound having a specificstructure has high solubility in a safe solvent, and is also capable offorming a radiation-sensitive composition which has high sensitivity andprovides a good resist pattern shape having small roughness; and reachedthe present invention.

More specifically, the present invention is as follows.

-   [1] A cyclic compound having a molecular weight of 500 to 5000 and    represented by the formula (1):

wherein R⁰ are each independently a hydrogen atom, a hydroxyl group, acyano group, a nitro group, a substituted or non-substitutedheterocyclic group, a halogen atom, a substituted or non-substitutedlinear aliphatic hydrocarbon group having 1 to 20 carbon atoms, asubstituted or non-substituted branched aliphatic hydrocarbon grouphaving 3 to 20 carbon atoms, a substituted or non-substituted cyclicaliphatic hydrocarbon group having 3 to 20 carbon atoms, a substitutedor non-substituted aryl group having 6 to 20 carbon atoms, a substitutedor non-substituted aralkyl group having 7 to 30 carbon atoms, asubstituted or non-substituted alkoxy group having 1 to 20 carbon atoms,a substituted or non-substituted amino group having 0 to 20 carbonatoms, a substituted or non-substituted alkenyl group having 2 to 20carbon atoms, a substituted or non-substituted acyl group having 1 to 20carbon atoms, a substituted or non-substituted alkoxycarbonyl grouphaving 2 to 20 carbon atoms, a substituted or non-substitutedalkyloyloxy group having 1 to 20 carbon atoms, a substituted ornon-substituted aryloyloxy group having 7 to 30 carbon atoms, asubstituted or non-substituted alkylsilyl group having 1 to 20 carbonatoms, or a group in which each of the groups is bonded to a bivalentgroup (one or more groups selected from the group consisting of asubstituted or non-substituted alkylene group, a substituted ornon-substituted allylene group, and an ether group); and

at least one of R⁰ is a monovalent group containing a (meth)acryloylgroup.

-   [2] The cyclic compound according to the above [1], wherein the    cyclic compound represented by the formula (1) is represented by the    formula (2):

wherein R¹ are each independently a hydrogen atom, a cyano group, anitro group, a substituted or non-substituted heterocyclic group, ahalogen atom, a substituted or non-substituted linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a substituted ornon-substituted branched aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, a substituted ornon-substituted aryl group having 6 to 20 carbon atoms, a substituted ornon-substituted alkylsilyl group having 1 to 20 carbon atoms, or asubstituted or non-substituted alkenyl group having 2 to 20 carbonatoms;

R² are each independently a hydrogen atom, a cyano group, a nitro group,a halogen atom, a substituted or non-substituted linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a substituted ornon-substituted branched aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, a substituted ornon-substituted aryl group having 6 to 20 carbon atoms, a substituted ornon-substituted aralkyl group having 7 to 30 carbon atoms, a substitutedor non-substituted alkoxy group having 1 to 20 carbon atoms, asubstituted or non-substituted alkenyl group having 2 to 20 carbonatoms, a substituted or non-substituted acyl group having 1 to 20 carbonatoms, a substituted or non-substituted alkoxycarbonyl group having 2 to20 carbon atoms, a substituted or non-substituted alkyloyloxy grouphaving 1 to 20 carbon atoms, a substituted or non-substituted aryloyloxygroup having 7 to 30 carbon atoms, or a substituted or non-substitutedalkylsilyl group having 1 to 20 carbon atoms;

R¹ are each independently a hydrogen atom, a substituted ornon-substituted linear aliphatic hydrocarbon group having 1 to 20 carbonatoms, a substituted or non-substituted branched aliphatic hydrocarbongroup having 3 to 20 carbon atoms, a substituted or non-substitutedcyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or agroup represented by the following formula (3):

wherein R⁴ are each independently a cyano group, a nitro group, asubstituted or non-substituted heterocyclic group, a halogen atom, asubstituted or non-substituted linear aliphatic hydrocarbon group having1 to 20 carbon atoms, a substituted or non-substituted branchedaliphatic hydrocarbon group having 3 to 20 carbon atoms, a substitutedor non-substituted cyclic aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted aryl group having 6 to 20carbon atoms, a substituted or non-substituted alkoxy group having 1 to20 carbon atoms, or a substituted or non-substituted alkylsilyl grouphaving 1 to 20 carbon atoms; p is an integer of 0 to 5; and

at least one of R¹ is a (meth)acryloyl group.

-   [3] The cyclic compound according to the above [2], wherein the    cyclic compound represented by the formula (2) is represented by the    formula (4):

wherein R¹ are each independently a hydrogen atom, a cyano group, anitro group, a substituted or non-substituted heterocyclic group, ahalogen atom, a substituted or non-substituted linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a substituted ornon-substituted branched aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, a substituted ornon-substituted aryl group having 6 to 20 carbon atoms, a substituted ornon-substituted alkylsilyl group having 1 to 20 carbon atoms, or asubstituted or non-substituted alkenyl group having 2 to 20 carbonatoms;

R⁴ are each independently a cyano group, a nitro group, a substituted ornon-substituted heterocyclic group, a halogen atom, a substituted ornon-substituted linear aliphatic hydrocarbon group having 1 to 20 carbonatoms, a substituted or non-substituted branched aliphatic hydrocarbongroup having 3 to 20 carbon atoms, a substituted or non-substitutedcyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, asubstituted or non-substituted aryl group having 6 to 20 carbon atoms, asubstituted or non-substituted alkoxy group having 1 to 20 carbon atoms,or a substituted or non-substituted alkylsilyl group having 1 to 20carbon atoms;

p is an integer of 0 to 5; and

at least one of R¹ is a (meth)acryloyl group.

-   [4] The cyclic compound according to the above [3], wherein the    cyclic compound represented by the formula (4) is represented by the    formula (5):

wherein R⁴ are each independently a cyano group, a nitro group, asubstituted or non-substituted heterocyclic group, a halogen atom, asubstituted or non-substituted linear aliphatic hydrocarbon group having1 to 20 carbon atoms, a substituted or non-substituted branchedaliphatic hydrocarbon group having 3 to 20 carbon atoms, a substitutedor non-substituted cyclic aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted aryl group having 6 to 20carbon atoms, a substituted or non-substituted alkoxy group having 1 to20 carbon atoms, or a substituted or non-substituted alkylsilyl grouphaving 1 to 20 carbon atoms;

p is an integer of 0 to 5; and

R⁵ is a (meth)acryloyl group.

-   [5] A method for producing the cyclic compound according to any one    of the above [1] to [4], comprising the steps of:

a condensation reaction of one or more aldehyde compounds (A1) with oneor more phenolic compounds (A2) to obtain a cyclic compound (A); and

a dehydrohalogenation reaction of the cyclic compound (A) with one ormore (meth)acryloyl halides.

-   [6] The method for producing the cyclic compound according to the    above [5], wherein:

the aldehyde compound (A1) has 1 to 4 formyl groups and has 1 to 59carbon atoms; and

the phenolic compound (A2) has 1 to 3 phenolic hydroxyl groups and has 6to 15 carbon atoms.

-   [7] A radiation-sensitive composition comprising a solid component    containing the cyclic compound according to any one of the above [1]    to [4] and a solvent.-   [8] The radiation-sensitive composition according to the above [7],    comprising 1 to 80% by weight of the solid component.-   [9] The radiation-sensitive composition according to the above [7]    or [8], wherein a content of the cyclic compound is 50 to 99.999% by    weight based on a total weight of the solid component.-   [10] The radiation-sensitive composition according to any one of the    above [7] to [9], further comprising an acid generating agent (C)    which directly or indirectly generates acid upon exposure to any    radiation selected from the group consisting of visible light,    ultraviolet, excimer laser, electron beam, extreme ultraviolet    (EUV), X-ray, and ion beam.-   [11] The radiation-sensitive composition according to any one of the    above [7] to [10], further comprising an acid crosslinking agent    (G).-   [12] The radiation-sensitive composition according to any one of the    above [7] to [11], further comprising an acid diffusion controlling    agent (E).-   [13] The radiation-sensitive composition according to any one of the    above [7] to [12], wherein the solid component comprises 50 to 99.4%    by weight of the cyclic compound, 0.001 to 49% by weight of an acid    generating agent (C), 0.5 to 49% by weight of an acid crosslinking    agent (G), and 0.001 to 49% by weight of an acid diffusion    controlling agent (E).-   [14] The radiation-sensitive composition according to any one of the    above [7] to [13], forming an amorphous film by spin coating.-   [15] The radiation-sensitive composition according to the above    [14], wherein a dissolution rate of the amorphous film into a    developing solution at 23° C. is 10 angstrom/sec or more.-   [16] The radiation-sensitive composition according to the above [14]    or [15], wherein a dissolution rate of the amorphous film into a    developing solution is 5 angstrom/sec or less after exposed to KrF    excimer laser, extreme ultraviolet, electron beam, or X-ray, or    after heated at 20 to 250° C.-   [17] A method for forming a resist pattern, comprising the steps of:

forming a resist film by coating a substrate with theradiation-sensitive composition according to any one of the above [7] to[16];

exposing the resist film; and

developing the exposed resist film.

Advantages of Invention

The present invention can provide a cyclic compound having highsolubility in a safe solvent and capable of forming aradiation-sensitive composition which has high sensitivity and providesa good resist pattern shape having small roughness, a method forproducing the cyclic compound, a radiation-sensitive compositioncontaining the cyclic compound, and a resist pattern formation methodusing the radiation-sensitive composition.

MODE FOR CARRYING OUT INVENTION

Hereinafter, an embodiment of the present invention (hereinafter, alsoreferred to as “present embodiment”) will be described in detail. Thefollowing embodiment is given in order to illustrate the presentinvention. The present invention is not limited to only the embodiment.

(Cyclic Compound and Production Method Thereof)

A cyclic compound of the present embodiment is a cyclic compound havinga molecular weight of 500 to 5000 and represented by the followingformula (1). The cyclic compound of the present embodiment is useful asa resist material.

In the formula (1), R⁰ are each independently a hydrogen atom, ahydroxyl group, a cyano group, a nitro group, a substituted ornon-substituted heterocyclic group, a halogen atom, a substituted ornon-substituted linear aliphatic hydrocarbon group having 1 to 20 carbonatoms, a substituted or non-substituted branched aliphatic hydrocarbongroup having 3 to 20 carbon atoms, a substituted or non-substitutedcyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, asubstituted or non-substituted aryl group having 6 to 20 carbon atoms, asubstituted or non-substituted aralkyl group having 7 to 30 carbonatoms, a substituted or non-substituted alkoxy group having 1 to 20carbon atoms, a substituted or non-substituted amino group having 0 to20 carbon atoms, a substituted or non-substituted alkenyl group having 2to 20 carbon atoms, a substituted or non-substituted acyl group having 1to 20 carbon atoms, a substituted or non-substituted alkoxycarbonylgroup having 2 to 20 carbon atoms, a substituted or non-substitutedalkyloyloxy group having 1 to 20 carbon atoms, a substituted ornon-substituted aryloyloxy group having 7 to 30 carbon atoms, asubstituted or non-substituted alkylsilyl group having 1 to 20 carbonatoms, or a group in which each of the groups is bonded to a bivalentgroup (one or more groups selected from the group consisting of asubstituted or non-substituted alkylene group, a substituted ornon-substituted allylene group, and an ether group); and at least one ofR⁰ is a monovalent group containing a (meth)acryloyl group.

At least one of R⁰ is a monovalent group containing a (meth)acryloylgroup, and thereby the cyclic compounds can be anionically polymerizedby an acid. As a result, the sensitivity of the radiation-sensitivecomposition (resist) containing the cyclic compound of the presentembodiment can be further improved. Particularly, in extreme ultraviolet(EUV) lithography, the high sensitivity of the resist is madeindispensable for improvement in productivity of a semiconductor device.The cyclic compound of the present embodiment is extremely useful.

Unless the circumstances are exceptional, “substitution” in the presentspecification means that one or more hydrogen atoms in a functionalgroup are substituted with a halogen atom, a hydroxyl group, a cyanogroup, a nitro group, a heterocyclic group, a linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a branched aliphatichydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms, an amino group having 0 to 20 carbonatoms, an alkenyl group having 2 to 20 carbon atoms, an acyl grouphaving 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20carbon atoms, an alkyloyloxy group having 1 to 20 carbon atoms, anaryloyloxy group having 7 to 30 carbon atoms, or an alkylsilyl grouphaving 1 to 20 carbon atoms.

Examples of the non-substituted heterocyclic group include, but notparticularly limited to, a pyridyl group, a bipyridyl group, apyrrolidyl group, a pyrazolyl group, an imidazolyl group, an isoxazolylgroup, an isothiazolyl group, a piperidyl group, a piperazyl group, amorpholyl group, a thiomorpholyl group, a triazole group, and atetrazole group.

Examples of the substituted heterocyclic group include, but notparticularly limited to, an N-methylpyridyl group, an N-fluoropyridylgroup, an N-hydroxypyridyl group, an N-cyanopyridyl group, amethylbipyridyl group, a methylpyrrolidyl group, a methylpyrazolylgroup, a methylimidazolyl group, a methylisoxazolyl group, amethylisothiazolyl group, a methylpiperidyl group, a methylpiperazylgroup, a methylmorpholyl group, a methylthiomorpholyl group, amethyltriazole group, and a methyltetrazole group.

Examples of the non-substituted linear aliphatic hydrocarbon grouphaving 1 to 20 carbon atoms include, but not particularly limited to, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, an octyl group, a decyl group, a dodecyl group, ahexadecyl group, and an octadecyl group.

Examples of the substituted linear aliphatic hydrocarbon group having 1to 20 carbon atoms include, but not particularly limited to, afluoromethyl group, a 2-hydroxyethyl group, a 3-cyanopropyl group, and a20-nitrooctadecyl group.

Examples of the non-substituted branched aliphatic hydrocarbon grouphaving 3 to 20 carbon atoms include, but not particularly limited to, anisopropyl group, an isobutyl group, a tertiary-butyl group, a neopentylgroup, a 2-hexyl group, a 2-octyl group, a 2-decyl group, a 2-dodecylgroup, a 2-hexadecyl group, and a 2-octadecyl group.

Examples of the substituted branched aliphatic hydrocarbon group having3 to 20 carbon atoms include, but not particularly limited to, a1-fluoroisopropyl group and a 1-hydroxy-2-octadecyl group.

Examples of the non-substituted cyclic aliphatic hydrocarbon grouphaving 3 to 20 carbon atoms include, but not particularly limited to, acyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexylgroup, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, acyclohexadecyl group, and a cyclooctadecyl group.

Examples of the substituted cyclic aliphatic hydrocarbon group having 3to 20 carbon atoms include, but not particularly limited to, a2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

Examples of the non-substituted aryl group having 6 to 20 carbon atomsinclude, but not particularly limited to, a phenyl group and a naphthylgroup.

Examples of the substituted aryl group having 6 to 20 carbon atomsinclude, but not particularly limited to, a 4-methylphenyl group and a6-fluoronaphthyl group.

Examples of the non-substituted aralkyl group having 7 to 30 carbonatoms include, but not particularly limited to, a methylphenyl group, anethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.

Examples of the substituted aralkyl group having 7 to 30 carbon atomsinclude, but not particularly limited to, a 4-fluoro-3-methylphenylgroup.

Examples of the non-substituted alkoxy group having 1 to 20 carbon atomsinclude, but not particularly limited to, a methoxy group, an ethoxygroup, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxygroup, an octyloxy group, a decyloxy group, a dodecyloxy group, ahexadecyloxy group, and an octadecyloxy group.

Examples of the substituted alkoxy group having 1 to 20 carbon atomsinclude, but not particularly limited to, a chloromethoxy group and abromoethoxy group.

Examples of the non-substituted amino group having 0 to 20 carbon atomsinclude, but not particularly limited to, an amino group, a methylaminogroup, a dimethylamino group, an ethylamino group, a diethylamino group,a dipropylamino group, and a dibutylamino group.

Examples of the substituted amino group having 0 to 20 carbon atomsinclude, but not particularly limited to, a chloromethylamino group anda dibromomethylamino group.

Examples of the non-substituted alkenyl group having 2 to 20 carbonatoms include, but not particularly limited to, a vinyl group, apropynyl group, a butynyl group, a pentynyl group, a hexynyl group, anoctynyl group, a decynyl group, a dodecynyl group, a hexadecynyl group,and an octadecynyl group.

Examples of the substituted alkenyl group having 2 to 20 carbon atomsinclude, but not particularly limited to, a chloropropynyl group.

Examples of the non-substituted acyl group having 1 to 20 carbon atomsinclude, but not particularly limited to, a formyl group, an acetylgroup, a propanoyl group, a butanoyl group, a pentanoyl group, ahexanoyl group, an octanoyl group, a decanoyl group, a dodecanoyl group,a hexadecanoyl group, and a benzoyl group, in addition to the(meth)acryloyl group.

Examples of the substituted acyl group having 1 to 20 carbon atomsinclude, but not particularly limited to, a chloroacetyl group.

Examples of the non-substituted alkoxycarbonyl group having 2 to 20carbon atoms include, but not particularly limited to, a methoxycarbonylgroup, an ethoxycarbonyl group, a propoxycarbonyl group, abutoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonylgroup, an octyloxycarbonyl group, a decyloxycarbonyl group, adodecyloxycarbonyl group, and a hexadecyloxycarbonyl group.

Examples of the substituted alkoxycarbonyl group having 2 to 20 carbonatoms include, but not particularly limited to, a chloromethoxycarbonylgroup.

Examples of the non-substituted alkyloyloxy group having 1 to 20 carbonatoms include, but not particularly limited to, a methoxycarbonyloxygroup, an ethoxycarbonyloxy group, a propoxycarbonyloxy group, abutoxycarbonyloxy group, a pentyloxycarbonyloxy group, ahexyloxycarbonyloxy group, an octyloxycarbonyloxy group, adecyloxycarbonyloxy group, a dodecyloxycarbonyloxy group, and ahexadecyloxycarbonyloxy group.

Examples of the substituted alkyloyloxy group having 1 to 20 carbonatoms include, but not particularly limited to, achloromethoxycarbonyloxy group.

Examples of the non-substituted aryloyloxy group having 7 to 30 carbonatoms include, but not particularly limited to, a benzoyloxy group and anaphthylcarbonyloxy group.

Examples of the substituted aryloyloxy group having 7 to 30 carbon atomsinclude, but not particularly limited to, a chlorobenzoyloxy group.

Examples of the non-substituted alkylsilyl group having 1 to 20 carbonatoms include, but not particularly limited to, a methylsilyl group, anethylsilyl group, a propylsilyl group, a butylsilyl group, a pentylsilylgroup, a hexylsilyl group, an octylsilyl group, a decylsilyl group, adodecylsilyl group, a hexadecylsilyl group, and an octadecylsilyl group.

Examples of the substituted alkylsilyl group having 1 to 20 carbon atomsinclude, but not particularly limited to, a chloromethylsilyl group.

Examples of the monovalent group containing a (meth)acryloyl groupinclude, but not particularly limited to, a (meth)acryloyl group, a(meth)acryloyloxy group, a linear aliphatic hydrocarbon group having 1to 6 carbon atoms substituted with the (meth)acryloyl group, a branchedaliphatic hydrocarbon group having 3 to 6 carbon atoms substituted withthe (meth)acryloyl group, a cyclic aliphatic hydrocarbon group having 3to 6 carbon atoms substituted with the (meth)acryloyl group, or an arylgroup having 6 carbon atoms substituted with the (meth)acryloyl group.

The cyclic compound represented by the formula (1) is preferably acompound represented by the formula (2).

In the formula (2), R¹ are each independently a hydrogen atom, a cyanogroup, a nitro group, a substituted or non-substituted heterocyclicgroup, a halogen atom, a substituted or non-substituted linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a substituted ornon-substituted branched aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, a substituted ornon-substituted aryl group having 6 to 20 carbon atoms, a substituted ornon-substituted alkylsilyl group having 1 to 20 carbon atoms, or asubstituted or non-substituted alkenyl group having 2 to 20 carbonatoms; R² are each independently a hydrogen atom, a cyano group, a nitrogroup, a halogen atom, a substituted or non-substituted linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a substituted ornon-substituted branched aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, a substituted ornon-substituted aryl group having 6 to 20 carbon atoms, a substituted ornon-substituted aralkyl group having 7 to 30 carbon atoms, a substitutedor non-substituted alkoxy group having 1 to 20 carbon atoms, asubstituted or non-substituted alkenyl group having 2 to 20 carbonatoms, a substituted or non-substituted acyl group having 1 to 20 carbonatoms, a substituted or non-substituted alkoxycarbonyl group having 2 to20 carbon atoms, a substituted or non-substituted alkyloyloxy grouphaving 1 to 20 carbon atoms, a substituted or non-substituted aryloyloxygroup having 7 to 30 carbon atoms, or a substituted or non-substitutedalkylsilyl group having 1 to 20 carbon atoms; R¹ are each independentlya hydrogen atom, a substituted or non-substituted linear aliphatichydrocarbon group having 1 to 20 carbon atoms, a substituted ornon-substituted branched aliphatic hydrocarbon group having 3 to 20carbon atoms, a substituted or non-substituted cyclic aliphatichydrocarbon group having 3 to 20 carbon atoms, or a group represented bythe following formula (3):

In the formula (3), R⁴ are each independently a cyano group, a nitrogroup, a substituted or non-substituted heterocyclic group, a halogenatom, a substituted or non-substituted linear aliphatic hydrocarbongroup having 1 to 20 carbon atoms, a substituted or non-substitutedbranched aliphatic hydrocarbon group having 3 to 20 carbon atoms, asubstituted or non-substituted cyclic aliphatic hydrocarbon group having3 to 20 carbon atoms, a substituted or non-substituted aryl group having6 to 20 carbon atoms, a substituted or non-substituted alkoxy grouphaving 1 to 20 carbon atoms, or a substituted or non-substitutedalkylsilyl group having 1 to 20 carbon atoms; p is an integer of 0 to 5;and at least one of R¹ is a (meth)acryloyl group.

The compound represented by the formula (2) is more preferably acompound represented by the formula (4):

The compound represented by the formula (4) has high solubility in asafe solvent, and can form a radiation-sensitive composition which hashigh sensitivity and provides a good resist pattern shape having smallroughness.

In the formula (4), R¹, R⁴ and p are the same as above.

Further, the compound represented by the formula (4) is still morepreferably a compound represented by the formula (5):

The compound represented by the formula (5) has high solubility in asafe solvent, and can form a radiation-sensitive composition which hashigh sensitivity and provides a good resist pattern shape having smallroughness.

In the formula (5), R⁴ and p are the same as above, and R⁵ is a(meth)acryloyl group.

The compound represented by the formula (4) is yet still more preferablya compound represented by the formula (6) or formula (7):

In the formula (6), R⁵ is the same as above.

In the formula (7), R⁵ is the same as above.

The compound represented by the formula (6) or (7) has higher solubilityin a safe solvent, and can form a radiation-sensitive composition whichhas higher sensitivity and provides a resist pattern having a bettershape having smaller roughness.

The molecular weight of the cyclic compound represented by the formula(1) is 500 to 5000, preferably 800 to 2000, and more preferably 1000 to2000. The above range can improve the resolution while maintaining thefilm forming property required when a resist is formed.

The cyclic compound of the present embodiment can be the cis form andthe trans form, but may be any one of forms or mixture of them. When thecyclic compound of the present embodiment is used as a resist componentof a radiation-sensitive composition, it is preferable to use only oneof the cis form and the trans form, because the uniformity of thecomponent within the resist film is high. A method for obtaining acyclic compound having only one of the cis form and the trans form canbe conducted by a publicly known methods such as separation by columnchromatography or preparative liquid chromatography, and optimization ofa reaction solvent and reaction temperature or the like upon production.

The cyclic compound of the present embodiment is obtained by aproduction method including the steps of: a condensation reaction of oneor more aldehyde compounds (A1) with one or more phenolic compounds (A2)to obtain a cyclic compound (A); and a dehydrohalogenation reaction ofthe cyclic compound (A) with one or more (meth)acryloyl halides.

Preferably, the cyclic compound of the present embodiment is obtained bya dehydrohalogenation reaction of a cyclic compound (A) obtained by acondensation reaction of one or more compounds selected from variousaromatic aldehyde compounds (A1A) with one or more compounds selectedfrom various phenol compounds (A2), with one or more compounds selectedfrom various (meth)acryloyl halides (A3).

The cyclic compound of the present embodiment can also be obtained by acondensation reaction of a phenol compound (A2A) obtained by adehydrohalogenation reaction of one or more compounds selected fromvarious phenol compounds (A2) with one or more compounds selected fromvarious (meth)acryloyl halides (A3), with one or more compounds selectedfrom various aldehyde compounds (A1).

The aldehyde compound (A1) preferably has 1 to 59 carbon atoms. Thealdehyde compound (A1) preferably has 1 to 4 formyl groups. The aldehydecompound (A1) is selected from an aromatic aldehyde compound (A1A) andan aliphatic aldehyde compound (A1B). The aromatic aldehyde compound(A1A) is preferably a benzaldehyde compound having 7 to 24 carbon atoms.Examples of the aromatic aldehyde compound (A1A) include, but notparticularly limited to, benzaldehyde, methylbenzaldehyde,dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde,butylbenzaldehyde, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde,diethylbenzaldehyde, anisaldehyde, naphthaldehyde, anthraldehyde,cyclopropylbenzaldehyde, cyclobutylbenzaldehyde,cyclopentylbenzaldehyde, cyclohexylbenzaldehyde, phenylbenzaldehyde,naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde,lactylbenzaldehyde, isopropylbenzaldehyde, normalpropylbenzaldehyde,bromobenzaldehyde, dimethylaminobenzaldehyde, hydroxybenzaldehyde,dihydroxybenzaldehyde, and trihydroxybenzaldehyde.Isopropylbenzaldehyde, normalpropylbenzaldehyde, cyclohexylbenzaldehyde,and phenylbenzaldehyde are preferable, and cyclohexylbenzaldehyde and4-isopropylbenzaldehyde are more preferable. The aromatic aldehydecompound (A1A) may have a linear or branched alkyl group having 1 to 4carbon atoms, a cyano group, a hydroxyl group, and a halogen or thelike, within the range of not deteriorating the effect of the presentinvention. The aromatic aldehyde compound (AlA) may be used alone or incombination of two or more kinds.

The aliphatic aldehyde compound (A1B) is preferably a compound having 1to 24 carbon atoms. Examples of the aliphatic aldehyde compound (A1B)include, but not particularly limited to, methanal, ethanal, propanal,isopropanal, butanal, isobutanal, t-butanal, pentanal, isopentanal,neopentanal, hexanal, isohexanal, octanal, decanal, dodecanal,undecenal, cyclopropanecarboxyaldehyde, cyclobutanecarboxyaldehyde, andcyclohexanecarboxyaldehyde. Isobutanal, t-butanal, pentanal,isopentanal, neopentanal, hexanal, isohexanal, octanal, decanal,dodecanal, cyclopropanecarboxyaldehyde, cyclobutanecarboxyaldehyde, andcyclohexanecarboxyaldehyde are preferable, and octanal, decanal,dodecanal, and cyclohexanecarboxyaldehyde are more preferable. Thealiphatic aldehyde compound (A1B) may have a cyano group, a hydroxylgroup, and a halogen or the like, within the range of not deterioratingthe effect of the present invention. The aliphatic aldehyde compound(A1B) may be used alone or in combination of two or more kinds.

The suitable phenolic compound (A2) preferably has 6 to 15 carbon atoms,and preferably has 1 to 3 phenolic hydroxyl groups. Examples of thephenolic compound (A2) include, but not particularly limited to, phenol,catechol, resorcinol, hydroquinone, and pyrogallol. Resorcinol, andpyrogallol are preferable, and resorcinol is more preferable. Thephenolic compound (A2) may have a linear or branched alkyl group having1 to 4 carbon atoms, a cyano group, a hydroxyl group, and a halogen orthe like, within the range of not deteriorating the effect of thepresent invention. The phenolic compound (A2) may be used alone or incombination of two or more kinds.

The (meth)acryloyl halide (A3) is preferably (meth)acryloyl chloride,(meth)acryloyl bromide, and (meth)acryloyl iodide, for example. The(meth)acryloyl halide (A3) may have a linear or branched alkyl grouphaving 1 to 4 carbon atoms, a cyano group, a hydroxyl group, and ahalogen or the like, within the range of not deteriorating the effect ofthe present invention. The (meth)acryloyl halide (A3) may be used aloneor in combination of two or more kinds.

For example, specifically, the cyclic compound of the present embodimentcan be produced by the following method. For example, 0.1 to 10 moles ofthe phenolic compound (A2) is reacted per mole of the aldehyde compound(A1) at 60 to 150° C. for about 0.5 to 20 hours in the presence of anacid catalyst (such as hydrochloric acid, sulfuric acid, or para-toluenesulfonic acid) in an organic solvent such as methanol or ethanol. Then,the reaction product is filtered, washed with alcohols such as methanol,washed with water, filtered to separate, and then dried, to obtain acyclic compound (A) having a molecular weight of preferably 700 to 5000.The cyclic compound (A) can also be obtained by using a basic catalyst(such as sodium hydroxide, barium hydroxide, or1,8-diazabicyclo[5.4.0]undecene-7) instead of the acid catalyst andreacting in the same way. Furthermore, the cyclic compound (A) can alsobe produced by treating the above aldehyde compound (A1) with hydrogenhalide or halogen gas into dihalide, and reacting the isolated dihalidewith the phenolic compound (A2).

Then, 1 mol of the cyclic compound (A) and 0.1 to 10 mol of the(meth)acryloyl halide (A3) are allowed to react at 0 to 150° C. forabout 0.5 to 20 hours in an organic solvent such asN-methyl-2-pyrrolidone, in the presence of a basic catalyst(triethylamine, ammonia, or sodium hydroxide or the like). By thisreaction, a phenolic hydroxyl group in the cyclic compound (A) can beconverted to a (meth)acryloyl group. Then, the reaction product isfiltered, washed with alcohols such as methanol, washed with water,filtered to separate, and then dried, to obtain the cyclic compoundrepresented by formula (1).

It is more preferable to use two or more of at least one of the aldehydecompound (A1) or the phenolic compound (A2) because the solubility ofthe resulting cyclic compound in a semiconductor safe solvent improves.

In the method for producing the cyclic compound, in order to improve thepurity of the cyclic compound, and to reduce the remaining metal amount,a purification step may be conducted if required. When an acid catalystand a co-catalyst remain, the storage stability of a radiation-sensitivecomposition generally decreases. When a basic catalyst remains, thesensitivity of a radiation-sensitive composition generally decreases.Therefore, purification for the purpose of reducing these catalysts maybe conducted.

The purification method can be conducted by any publicly known methodunless a cyclic compound is modified. Examples thereof include, but notparticularly limited to, methods of washing with water, washing with anacid aqueous solution, washing with a basic aqueous solution, treatingwith an ion exchange resin, and treating by silica gel columnchromatography. It is more preferable to conduct these purificationmethods in combination of two or more kinds. It is possible toarbitrarily select the optimal one for the acid aqueous solution, thebasic aqueous solution, the ion exchange resin, and the silica gelcolumn chromatography, according to the amount and kind of metal, acidiccompound and basic compound to be removed, and the kind of cycliccompound to be purified or the like. Examples of the acid aqueoussolution include aqueous solutions of hydrochloric acid, nitric acid,and acetic acid with a concentration of 0.01 to 10 mol/L. Examples ofthe basic aqueous solution include an aqueous solution of ammonia with aconcentration of 0.01 to 10 mol/L. Examples of the ion exchange resininclude a cation exchange resin such as Amberlyst 15J-HG Drymanufactured by Organo. Drying may be conducted after purification.Drying can be conducted by a publicly known method. Examples of themethod include, but not particularly limited to, methods of vacuumdrying and hot air drying under the condition where a cyclic compound isnot modified.

When the cyclic compound of the present embodiment is used as thecomponent of the radiation-sensitive composition, an amorphous film canbe formed by spin coating. The cyclic compound of the present embodimentcan be applied to a typical semiconductor production process.

The cyclic compound of the present embodiment is useful as a negativetype resist material which becomes a hardly soluble compound in adeveloping solution by being irradiated with KrF excimer laser, extremeultraviolet, electron beam, or X-ray. A mechanism in which the cycliccompound of the present embodiment is a compound hardly soluble in adeveloping solution is not clear. However, by irradiating the cycliccompound with KrF excimer laser, extreme ultraviolet, electron beam, orX-ray, a condensation reaction among the compounds is considered to beinduced to provide a compound hardly soluble in an alkaline developingsolution. Thus, a resist pattern obtained by using the cyclic compoundof the present embodiment has very small line edge roughness (LER).

Further, the cyclic compound of the present embodiment can be used as amain component of a negative type radiation-sensitive composition.Moreover, the cyclic compound can be added to a radiation-sensitivecomposition as an additive agent for improving sensitivity and etchingresistance, for example. In this case, the amount of the cyclic compoundof the present embodiment used as an additive agent is preferably 1 to49.999% by weight of the total weight of the solid component of theradiation-sensitive composition.

The glass transition temperature of the cyclic compound of the presentembodiment is preferably 100° C. or more, more preferably 120° C. ormore, still more preferably 140° C. or more, and particularly preferably150° C. or more. By having the glass transition temperature within theabove range, in a semiconductor lithography process, it has heatresistance capable of maintaining the pattern shape, and improvedperformance such as high resolution.

The crystallization heat generation amount obtained by differentialscanning calorimetrical analysis of the glass transition temperature ofthe cyclic compound of the present embodiment is preferably less than 20J/g. In the cyclic compound of the present embodiment, (crystallizationtemperature)−(glass transition temperature) is preferably 70° C. ormore, more preferably 80° C. or more, still more preferably 100° C. ormore, and particularly preferably 130° C. or more. When thecrystallization heat generation amount is less than 20 J/g or(crystallization temperature)−(glass transition temperature) is withinthe above range, by spin coating with a radiation-sensitive composition,an amorphous film is easily formed; the film forming property requiredfor a resist can be maintained over an extended period of time; and theresolution can be further improved.

In the present embodiment, the crystallization heat generation amount,the crystallization temperature, and the glass transition temperaturecan be obtained by differential scanning calorimetrical analysis usingDSC/TA-50WS manufactured by Shimadzu Corporation as follows. About 10 mgof the sample is placed in a non-sealed container made of aluminum, andthe temperature is raised to the melting point or more at the rate oftemperature rise of 20° C./min in a nitrogen gas stream (50 mL/min).After quenching, again the temperature is raised to the melting point ormore at the rate of temperature rise of 20° C./min in a nitrogen gasstream (30 mL/min). After further quenching, again the temperature israised to 400° C. at the rate of temperature rise of 20° C./min in anitrogen gas stream (30 mL/min). The temperature at the middle point ofthe step of the baseline stepwisely changed (where the specific heat ischanged into the half) is defined as the glass transition temperature(Tg), and the temperature at the subsequently appearing heat generationpeak is defined as the crystallization temperature. The heat generationamount is obtained from the area of the region surrounded by the heatgeneration peak and the baseline, as the crystallization heat generationamount.

The cyclic compound of the present embodiment preferably has a lowsublimation property under normal pressure at 100° C. or less,preferably 120° C. or less, more preferably 130° C. or less, still morepreferably 140° C. or less, and particularly preferably 150° C. or less.Herein, the low sublimation property means that the weight decreaseafter being kept at a predetermined temperature for 10 minutes inthermogravimetrical analysis is 10% or less, preferably 5% or less, morepreferably 3% or less, still more preferably 1% or less, andparticularly preferably 0.1% or less. Contamination of an exposureequipment by outgas upon exposure can be prevented by the lowsublimation property. Also, a good pattern shape with low LER can beobtained.

The cyclic compound of the present embodiment is preferably F<3.0 (Frepresents total atom number/(total carbon atom number-total oxygen atomnumber)), and more preferably F<2.5. By meeting the above condition, thecyclic compound of the present embodiment has excellent dry etchingresistance.

The cyclic compound of the present embodiment dissolves in a solventselected from propylene glycol monomethyl ether acetate (PGMEA),propylene glycol monomethyl ether (PGME), cyclohexanone (CHN),cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethylpropionate, and ethyl lactate, and showing the highest dissolvingability to the cyclic compound, in preferably 1% by mass or more, morepreferably 5% by mass or more, and still more preferably 10% by mass ormore at 23° C. Among these, the cyclic compound of the presentembodiment dissolves in a solvent selected from PGMEA, PGME and CHN, andshowing the highest dissolving ability to the cyclic compound, inpreferably 20% by mass or more at 23° C., and particularly preferably inPGMEA in 20% by mass or more at 23° C. When the above conditions aremet, the use of the cyclic compound of the present embodiment in asemiconductor production process in the actual production becomespossible.

A nitrogen atom may be introduced into the cyclic compound of thepresent embodiment, within the range of not deteriorating the effect ofthe present invention. The percentage of the number of nitrogen atoms tothe number of all constituent atoms of the cyclic compound is preferably0.1 to 40%, more preferably 0.1 to 20%, still more preferably 0.1 to10%, and particularly preferably 0.1 to 5%. When the percentage of thenumber of nitrogen atoms to the number of all constituent atoms of thecyclic compound is within the above range, the line edge roughness ofthe obtained resist pattern can be reduced. The nitrogen atom introducedinto the cyclic compound of the present embodiment is preferably asecondary nitrogen atom or a tertiary nitrogen atom, and more preferablya tertiary nitrogen atom.

A crosslinking reactive group initiating a crosslinking reaction byvisible light, ultraviolet, excimer laser, electron beam, extremeultraviolet (EUV), X-ray, and ion beam irradiation or a chemicalreaction induced thereby may be introduced into the cyclic compound ofthe present embodiment, within the range of not deteriorating the effectof the present invention. The introduction of a crosslinking reactivegroup into the cyclic compound of the present embodiment is conductedby, for example, reacting the cyclic compound with the crosslinkingreactive group introducing agent in the presence of a basic catalyst.Examples of the crosslinking reactive group include, but notparticularly limited to, a carbon-carbon multiple bond, an epoxy group,an azide group, a halogenated phenyl group, and a chloromethyl group.Examples of the crosslinking reactive group introducing agent include,but not particularly limited to, an acid having such a crosslinkingreactive group, acid chloride, acid anhydride, a carboxylic acidderivative such as dicarbonate, and alkyl halide. A radiation-sensitivecomposition containing a cyclic compound having a crosslinking reactivegroup is also useful as a non-polymeric radiation-sensitive compositionwith high resolution, high heat resistance, and solvent solubility.

A nonacid dissociation functional group may be introduced into at leastone phenolic hydroxyl group of the cyclic compound of the presentembodiment, within the range of not deteriorating the effect of thepresent invention. The nonacid dissociation functional group refers to acharacteristic group not cleaving in the presence of an acid and notgenerating an alkali soluble group. Examples of the nonacid dissociationfunctional group include a functional group selected from the groupconsisting of an alkyl group having C1 to 20, a cycloalkyl group havingC3 to 20, an aryl group having C6 to 20, an alkoxyl group having C1 to20, a cyano group, a nitro group, a hydroxyl group, a heterocyclicgroup, halogen, a carboxyl group, alkylsilane of C1 to 20, and aderivative thereof, which are not degraded by action of an acid.

A naphthoquinone diazide ester group may be introduced into at least onephenolic hydroxyl group of the cyclic compound of the presentembodiment, within the range of not deteriorating the effect of thepresent invention. A cyclic compound having a naphthoquinone diazideester group introduced into at least one phenolic hydroxyl group of thecyclic compound, as a main component itself, can be used as a maincomponent of a negative type radiation-sensitive composition. Moreover,the cyclic compound can be used as a main component of a positive typeradiation-sensitive composition, and can be added to aradiation-sensitive composition, as an acid generating agent and anadditive agent.

An acid generating functional group generating an acid by irradiation ofradiation may be introduced into at least one phenolic hydroxyl group ofthe cyclic compound of the present embodiment, within the range of notdeteriorating the effect of the present invention. A cyclic compoundhaving an acid generating functional group introduced into at least onephenolic hydroxyl group of the cyclic compound, as a main componentitself, can be used as a main component of a negative typeradiation-sensitive composition. Moreover, the cyclic compound can beadded to a radiation-sensitive composition as an additive agent.

(Radiation-Sensitive Composition)

The radiation-sensitive composition of the present embodiment contains asolid component containing the above cyclic compound and, a solvent. Theradiation-sensitive composition of the present embodiment comprisespreferably 1 to 80% by weight of the solid component. Furthermore, thecontent of the cyclic compound is preferably 50 to 99.999% by weightbased on the total weight of the solid component.

The radiation-sensitive composition of the present embodiment can forman amorphous film by spin coating. The dissolution rate of the amorphousfilm formed by spin coating the radiation-sensitive composition of thepresent embodiment in a developing solution at 23° C. is preferably 10angstrom/sec or more, more preferably 10 to 10000 angstrom/sec, andstill more preferably 100 to 1000 angstrom/sec. When the dissolutionrate of the radiation-sensitive composition of the present embodiment is10 angstrom/sec or more, it can dissolve in the developing solution tobe a resist. When the radiation-sensitive composition of the presentembodiment has the dissolution rate of 10000 angstrom/sec or less, theresolution may improve. It is presumed that this is because due to thechange in the solubility before and after exposure of the cycliccompound, contrast at the interface between the unexposed portion beingdissolved in a developing solution and the exposed portion not beingdissolved in a developing solution is increased. There are reductioneffects of LER and defect.

The dissolution rate of the portion exposed by radiation such as KrFexcimer laser, extreme ultraviolet, electron beam or X-ray, of theamorphous film formed by spin coating with the radiation-sensitivecomposition of the present embodiment, in a developing solution at 23°C. is preferably 5 angstrom/sec or less, more preferably 0.05 to 5angstrom/sec, and still more preferably 0.0005 to 5 angstrom/sec. Whenthe radiation-sensitive composition of the present embodiment has thedissolution rate of 5 angstrom/sec or less, the radiation-sensitivecomposition is insoluble in a developing solution, and is suitably usedfor a resist. When the radiation-sensitive composition of the presentembodiment has the dissolution rate of 0.0005 angstrom/sec or more, theresolution may improve. It is presumed that this is because the microsurface portion of the cyclic compound dissolves and LER is reduced.There is also a reduction effect of defect.

As described above, the radiation-sensitive composition of the presentembodiment preferably contains 1 to 80% by weight of the solid componentand 20 to 99% by weight of the solvent, more preferably contains 1 to50% by weight of the solid component and 50 to 99% by weight of thesolvent, still more preferably 2 to 40% by weight of the solid componentand 60 to 98% by weight of the solvent, and particularly preferably 2 to10% by weight of the solid component and 90 to 98% by weight of thesolvent.

In the radiation-sensitive composition of the present embodiment, theamount of the above cyclic compound is preferably 50 to 99.4% by weightof the total weight of the solid component (summation of optionally usedsolid component such as the above cyclic compound, acid generating agent(C), acid crosslinking agent (G), acid diffusion controlling agent (E),and other component (F) to be described below, hereinafter the same),more preferably 55 to 90% by weight, still more preferably 60 to 80% byweight, and particularly preferably 60 to 70% by weight. When thecontent of the above cyclic compound in the radiation-sensitivecomposition of the present embodiment is within the above range, highresolution is obtained and line edge roughness becomes small.

The radiation-sensitive composition of the present embodiment preferablycontains one or more acid generating agents (C) generating an aciddirectly or indirectly by irradiation of any radiation selected fromvisible light, ultraviolet, excimer laser, electron beam, extremeultraviolet (EUV), X-ray, and ion beam. The content of the acidgenerating agent (C) is preferably 0.001 to 49% by weight of the totalweight of the solid component, more preferably 1 to 40% by weight, stillmore preferably 3 to 30% by weight, and particularly preferably 10 to25% by weight. When the content of the acid generating agent (C) in theradiation-sensitive composition of the present embodiment is within theabove range, a pattern profile with high sensitivity and low edgeroughness is obtained. In the present embodiment, the acid generationmethod is not limited as long as an acid is generated within a system.By using excimer laser instead of ultraviolet such as g-ray and i-ray,finer processing is possible, and also by using electron beam, extremeultraviolet, X-ray or ion beam as a high energy ray, further finerprocessing is possible.

The acid generating agent (C) is preferably at least one kind selectedfrom the group consisting of compounds represented by the followingformulae (7-1) to (7-8):

In the formula (7-1), R¹³ may be the same or different, and are eachindependently a hydrogen atom, a linear, branched or cyclic alkyl group,a linear, branched or cyclic alkoxy group, a hydroxyl group, or ahalogen atom; X⁻ is an alkyl group, an aryl group, a sulfonic acid ionhaving a halogen substituted alkyl group or a halogen substituted arylgroup, or a halide ion.

The compound represented by the above formula (7-1) is preferably atleast one kind selected from the group consisting of triphenylsulfoniumtrifluoromethanesulfonate, triphenylsulfoniumnonafluoro-n-butanesulfonate, diphenyltolylsulfoniumnonafluoro-n-butanesulfonate, triphenylsulfoniumperfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfoniumtrifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfoniumtrifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfoniumtrifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfoniumnonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfoniumtrifluoromethanesulfonate, bis(4-fluorophenyl)-4-hydroxyphenylsulfoniumtrifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfoniumnonafluoro-n-butanesulfonate, bis(4-hydroxyphenyl)-phenylsulfoniumtrifluoromethanesulfonate, tri(4-methoxyphenyl)sulfoniumtrifluoromethanesulfonate, tri(4-fluorophenyl)sulfoniumtrifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate,triphenylsulfonium benzenesulfonate,diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate,diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate,diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate,diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate,diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate,diphenylnaphthylsulfonium trifluoromethanesulfonate,diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate,triphenylsulfonium-10-camphorsulfonate,diphenyl-4-hydroxyphenylsulfonium-10-camphorsulfonate, andcyclo(1,3-perfluoropropanedisulfone)imidate.

In the formula (7-2), R¹⁴ may be the same or different, and eachindependently represents a hydrogen atom, a linear, branched or cyclicalkyl group, a linear, branched or cyclic alkoxy group, a hydroxylgroup, or a halogen atom. X⁻ is the same as above.

The compound represented by the above formula (7-2) is preferably atleast one kind selected from the group consisting ofbis(4-t-butylphenyl)iodonium trifluoromethanesulfonate,bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate,bis(4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate,bis(4-t-butylphenyl)iodonium p-toluenesulfonate,bis(4-t-butylphenyl)iodonium benzenesulfonate,bis(4-t-butylphenyl)iodonium-2-trifluoromethylbenzenesulfonate,bis(4-t-butylphenyl)iodonium-4-trifluoromethylbenzenesulfonate,bis(4-t-butylphenyl)iodonium-2,4-difluorobenzenesulfonate,bis(4-t-butylphenyl)iodonium hexafluorobenzenesulfonate,bis(4-t-butylphenyl)iodonium-10-camphorsulfonate, diphenyliodoniumtrifluoromethanesulfonate, diphenyliodoniumnonafluoro-n-butanesulfonate, diphenyliodoniumperfluoro-n-octanesulfonate, diphenyliodonium p-toluenesulfonate,diphenyliodonium benzenesulfonate, diphenyliodonium-10-camphorsulfonate,diphenyliodonium-2-trifluoromethylbenzenesulfonate,diphenyliodonium-4-trifluoromethylbenzenesulfonate,diphenyliodonium-2,4-difluorobenzenesulfonate, diphenyliodoniumhexafluorobenzenesulfonate, di(4-trifluoromethylphenyl)iodoniumtrifluoromethanesulfonate, di(4-trifluoromethylphenyl)iodoniumnonafluoro-n-butanesulfonate, di(4-trifluoromethylphenyl)iodoniumperfluoro-n-octanesulfonate,di(4-trifluoromethylphenyl)iodonium-p-toluenesulfonate,di(4-trifluoromethylphenyl)iodonium benzenesulfonate, anddi(4-trifluoromethylphenyl)iodonium-10-camphersulfonate.

In the formula (7-3), Q is an alkylene group, an arylene group, or analkoxylene group, and R¹⁵ is an alkyl group, an aryl group, a halogensubstituted alkyl group, or a halogen substituted aryl group.

The compound represented by the above formula (7-3) is preferably atleast one kind selected from the group consisting ofN-(trifluoromethylsulfonyloxy)succinimide,N-(trifluoromethylsulfonyloxy)phthalimide,N-(trifluoromethylsulfonyloxy)diphenylmaleimide,N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(trifluoromethylsulfonyloxy)naphthylimide,N-(10-camphorsulfonyloxy)succinimide,N-(10-camphorsulfonyloxy)phthalimide,N-(10-camphorsulfonyloxy)diphenylmaleimide,N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(10-camphorsulfonyloxy)naphthylimide,N-(n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(n-octanesulfonyloxy)naphthylimide,N-(p-toluenesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(p-toluenesulfonyloxy)naphthylimide,N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(2-trifluoromethylbenzenesulfonyloxy)naphthylimide,N-(4-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(4-trifluoromethylbenzenesulfonyloxy)naphthylimide,N-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(perfluorobenzenesulfonyloxy)naphthylimide,N-(1-naphthalenesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(1-naphthalenesulfonyloxy)naphthylimide,N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,N-(nonafluoro-n-butanesulfonyloxy)naphthylimide,N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxyimide,and N-(perfluoro-n-octanesulfonyloxy)naphthylimide.

In the formula (7-4), R¹⁶ may be the same or different, and are eachindependently an optionally substituted linear, branched or cyclic alkylgroup, an optionally substituted aryl group, an optionally substitutedheteroaryl group, or an optionally substituted aralkyl group.

The compound represented by the above formula (7-4) is preferably atleast one kind selected from the group consisting of diphenyldisulfone,di(4-methylphenyl)disulfone, dinaphthyldisulfone,di(4-tert-butylphenyl)disulfone, di(4-hydroxyphenyl)disulfone,di(3-hydroxynaphthyl)disulfone, di(4-fluorophenyl)disulfone,di(2-fluorophenyl)disulfone, and di(4-trifluoromethylphenyl)disulfone.

In the formula (7-5), R¹⁷ may be the same or different, and are eachindependently an optionally substituted linear, branched or cyclic alkylgroup, an optionally substituted aryl group, an optionally substitutedheteroaryl group, or an optionally substituted aralkyl group.

The compound represented by the above formula (7-5) is preferably atleast one kind selected from the group consisting ofα-(methylsulfonyloxyimino)-phenylacetonitrile,α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile,α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile,α-(trifluoromethylsulfonyloxyimino)-4-methoxyphenylacetonitrile,α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile,α-(propylsulfonyloxyimino)-4-methylphenylacetonitrile, andα-(methylsulfonyloxyimino)-4-bromophenylacetonitrile.

In the formula (7-6), R¹⁸ may be the same or different, and are eachindependently a halogenated alkyl group having one or more chlorineatoms and one or more bromine atoms. The number of carbon atoms of thehalogenated alkyl group is preferably 1 to 5.

In the formulae (7-7) and (7-8), R¹⁹ and R²⁰ are each independently analkyl group having 1 to 3 carbon atoms such as a methyl group, an ethylgroup, an n-propyl group, and an isopropyl group; a cycloalkyl groupsuch as a cyclopentyl group and a cyclohexyl group; an alkoxyl grouphaving 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, anda propoxy group; or an aryl group such as a phenyl group, a toluoylgroup, and a naphthyl group, and preferably an aryl group having 6 to 10carbon atoms. L¹⁹ and L²⁰ are each independently an organic group havinga 1,2-naphthoquinonediazide group. Specifically, preferable examples ofthe organic group having a 1,2-naphthoquinonediazide group include a1,2-quinonediazidesulfonyl group such as a1,2-naphthoquinonediazide-4-sulfonyl group, a1,2-naphthoquinonediazide-5-sulfonyl group, and a1,2-naphthoquinonediazide-6-sulfonyl group. Particularly, a1,2-naphthoquinonediazide-4-sulfonyl group and a1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is aninteger of 1 to 3; q is an integer of 0 to 4; and 1≦p+q≦5. J¹⁹ is asingle bond, a polymethylene group having 1 to 4 carbon atoms, acycloalkylene group, a phenylene group, a group represented by thefollowing formula (7-7-1), a carbonyl group, an ester group, an amidegroup, or an ether group. Y¹⁹ is a hydrogen atom, an alkyl group, or anaryl group, and X²⁰ are each independently a group represented by thefollowing formula (7-8-1):

In the formula (7-8-1), Z²² are each independently an alkyl group, acycloalkyl group, or an aryl group; R²² is an alkyl group, a cycloalkylgroup, or an alkoxyl group; and r is an integer of 0 to 3.

Examples of the other acid generating agent include, but notparticularly limited to, bissulfonyldiazomethanes such asbis(p-toluenesulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane,bis(tert-butylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane,bis(isobutylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane,bis(n-propylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane,bis(isopropylsulfonyl)diazomethane,1,3-bis(cyclohexylsulfonylazomethylsulfonyl)propane,1,4-bis(phenylsulfonylazomethylsulfonyl)butane,1,6-bis(phenylsulfonylazomethylsulfonyl)hexane, and1,10-bis(cyclohexylsulfonylazomethylsulfonyl)decane; andhalogen-containing triazine derivatives such as2-(4-methoxyphenyl)-4,6-(bistrichloromethyl)-1,3,5-triazine,2-(4-methoxynaphthyl)-4,6-(bistrichloromethyl)-1,3,5-triazine,tris(2,3-dibromopropyl)-1,3,5-triazine, andtris(2,3-dibromopropyl)isocyanurate.

Among the above acid generating agents, an acid generating agent havingan aromatic ring is preferable, and an acid generating agent representedby the formula (7-1) or (7-2) is more preferable. An acid generatingagent having a sulfonate ion wherein X⁻ of the formula (7-1) or (7-2)has an aryl group or a halogen-substituted aryl group is still morepreferable; an acid generating agent having a sulfonate ion having anaryl group is particularly preferable; anddiphenyltrimethylphenylsulfonium-p-toluenesulfonate,triphenylsulfonium-p-toluenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate, and triphenylsulfoniumnonafluoromethanesulfonate are particularly preferable. By using theacid generating agent, LER can be further reduced.

The above acid generating agent (C) can be used alone or in combinationof two or more kinds.

The radiation-sensitive composition of the present embodiment preferablycontains one or more acid crosslinking agents (G). The acid crosslinkingagent (G) is a compound capable of intramolecular or intermolecularcrosslinking the cyclic compound described above in the presence of theacid generated from the acid generating agent (C). Examples of such anacid crosslinking agent (G) include a compound having one or more groups(hereinafter, referred to as “crosslinkable group”) capable ofcrosslinking the cyclic compound of the formula (1).

Specific examples of such a crosslinkable group include, but notparticularly limited to, (i) a hydroxyalkyl group such as a hydroxy(C1-C6 alkyl group), a C1-C6 alkoxy (C1-C6 alkyl group), and an acetoxy(C1-C6 alkyl group), or a group derived therefrom; (ii) a carbonyl groupsuch as a formyl group and a carboxy (C1-C6 alkyl group), or a groupderived therefrom; (iii) a nitrogenous group-containing group such as adimethylaminomethyl group, a diethylaminomethyl group, adimethylolaminomethyl group, a diethylolaminomethyl group, and amorpholinomethyl group; (iv) a glycidyl group-containing group such as aglycidyl ether group, a glycidyl ester group, and a glycidylamino group;(v) a group derived from an aromatic group such as a C1-C6 allyloxy(C1-C6 alkyl group) and a C1-C6 aralkyloxy (C1-C6 alkyl group) such as abenzyloxymethyl group and a benzoyloxymethyl group; and (vi) apolymerizable multiple bond-containing group such as a vinyl group and aisopropenyl group. As the crosslinkable group of the acid crosslinkingagent (G) used in the present embodiment, a hydroxyalkyl group and analkoxyalkyl group or the like are preferable, and an alkoxymethyl groupis particularly preferable.

Examples of the acid crosslinking agent (G) having the abovecrosslinkable group include, but not particularly limited to, (i) amethylol group-containing compound such as a methylol group-containingmelamine compound, a methylol group-containing benzoguanamine compound,a methylol group-containing urea compound, a methylol group-containingglycoluryl compound, and a methylol group-containing phenolic compound;(ii) an alkoxyalkyl group-containing compound such as an alkoxyalkylgroup-containing melamine compound, an alkoxyalkyl group-containingbenzoguanamine compound, an alkoxyalkyl group-containing urea compound,an alkoxyalkyl group-containing glycoluryl compound, and an alkoxyalkylgroup-containing phenolic compound; (iii) a carboxymethylgroup-containing compound such as a carboxymethyl group-containingmelamine compound, a carboxymethyl group-containing benzoguanaminecompound, a carboxymethyl group-containing urea compound, acarboxymethyl group-containing glycoluryl compound, and a carboxymethylgroup-containing phenolic compound; (iv) an epoxy compound such as abisphenol A based epoxy compound, a bisphenol F based epoxy compound, abisphenol S based epoxy compound, a novolac resin based epoxy compound,a resol resin based epoxy compound, and a poly(hydroxystyrene) basedepoxy compound.

As the acid crosslinking agent (G), a compound having a phenolichydroxyl group, and a compound or resin where the above crosslinkablegroup is introduced into an acid functional group in an alkali solubleresin to impart crosslinkability can be further used. The introductionrate of the crosslinkable group in that case is adjusted to be normally5 to 100 mol %, preferably 10 to 60 mol %, and more preferably 15 to 40mol % based on the total acid functional groups in the compound having aphenolic hydroxyl group, and the alkali soluble resin. By having theintroduction rate of the crosslinkable group within the above range, thecrosslinking reaction sufficiently occurs, and a decrease in the filmremaining rate, and swelling phenomena and meandering or the like of apattern can be avoided, which is preferable.

In the radiation-sensitive composition of the present embodiment, as theacid crosslinking agent (G), an alkoxyalkylated urea compound or resinthereof, or an alkoxyalkylated glycoluryl compound or resin thereof ispreferable. Particularly preferable examples of the acid crosslinkingagent (G) include compounds represented by the following formulae (8-1)to (8-3) and an alkoxymethylated melamine compound (acid crosslinkingagent (G1)).

In the above formulae (8-1) to (8-3), R⁷ each independently represents ahydrogen atom, an alkyl group, or an acyl group; R⁸ to R¹¹ eachindependently represents a hydrogen atom, a hydroxyl group, an alkylgroup, or an alkoxyl group; and X² represents a single bond, a methylenegroup, or an oxygen atom.

The number of carbon atoms of the alkyl group represented by R⁷ ispreferably 1 to 6, and more preferably 1 to 3. Examples thereof includea methyl group, an ethyl group, and a propyl group. The number of carbonatoms of the acyl group represented by R⁷ is preferably 2 to 6, and morepreferably 2 to 4. Examples thereof include an acetyl group and apropyonyl group. The number of carbon atoms of the alkyl grouprepresented by R⁸ to R¹¹ is preferably 1 to 6, and more preferably 1 to3. Examples thereof include a methyl group, an ethyl group, and a propylgroup. The number of carbon atoms of the alkoxy group represented by R⁸to R¹¹ is preferably 1 to 6, and more preferably 1 to 3. Examplesthereof include a methoxy group, an ethoxy group, and a propoxy group.X² is preferably a single bond or a methylene group. R⁷ to R¹¹ and X²may be substituted with an alkyl group such as a methyl group and anethyl group, an alkoxy group such as a methoxy group and an ethoxygroup, a hydroxyl group, and a halogen atom or the like. A plurality ofR⁷ and R⁸ to R¹¹ may be each the same or different.

Specific examples of the compound represented by the formula (8-1)include, but not particularly limited to, compounds shown below:

Specific examples of the compound represented by the formula (8-2)include, but not particularly limited to,N,N,N,N-tetra(methoxymethyl)glycoluryl,N,N,N,N-tetra(ethoxymethyl)glycoluryl,N,N,N,N-tetra(n-propoxymethyl)glycoluryl,N,N,N,N-tetra(isopropoxymethyl)glycoluryl,N,N,N,N-tetra(n-butoxymethyl)glycoluryl, andN,N,N,N-tetra(t-butoxymethyl)glycoluryl. Among them, particularly,N,N,N,N-tetra(methoxymethyl)glycoluryl is preferable.

Specific examples of the compound represented by the formula (8-3)include, but not particularly limited to, compounds shown below:

Specific examples of the alkoxymethylated melamine compound includeN,N,N,N,N,N-hexa(methoxymethyl)melamine,N,N,N,N,N,N-hexa(ethoxymethyl)melamine,N,N,N,N,N,N-hexa(n-propoxymethyl)melamine,N,N,N,N,N,N-hexa(isopropoxymethyl)melamine,N,N,N,N,N,N-hexa(n-butoxymethyl)melamine, andN,N,N,N,N,N-hexa(t-butoxymethyl)melamine. Among them, particularly,N,N,N,N,N,N-hexa(methoxymethyl)melamine is preferable.

The above acid crosslinking agent (G1) can be obtained by, for example,conducting a condensation reaction of a urea compound or a glycolurylcompound with formalin to introduce an methylol group, etherifying theproduct with lower alcohols such as methyl alcohol, ethyl alcohol,propyl alcohol, and butyl alcohol, and then cooling the reactionsolution to collect a precipitated compound or resin thereof. The aboveacid crosslinking agent (G1) can be obtained as a commercially availableproduct such as CYMEL (trade name, manufactured by MT AquaPolymer) andNIKALAC (manufactured by Sanwa Chemical).

Other particularly preferable examples of the acid crosslinking agent(G) include a phenol derivative having 1 to 6 benzene rings within amolecule and two or more hydroxyalkyl groups and/or alkoxyalkyl groupswithin the entire molecule, the hydroxyalkyl groups and/or alkoxyalkylgroups being bonded to any of the above benzene rings (acid crosslinkingagent (G2)). Preferable examples thereof include a phenol derivativehaving a molecular weight of 1500 or less, 1 to 6 benzene rings and atotal of two or more hydroxyalkyl groups and/or alkoxyalkyl groupswithin a molecule, the hydroxyalkyl groups and/or alkoxyalkyl groupsbeing bonded to any one of the above benzene rings, or a plurality ofbenzene rings.

As the hydroxyalkyl group bonded to a benzene ring, the one having 1 to6 carbon atoms such as a hydroxymethyl group, a 2-hydroxyethyl group,and a 2-hydroxy-1-propyl group is preferable. As the alkoxyalkyl groupbonded to a benzene ring, the one having 2 to 6 carbon atoms ispreferable. Specifically, a methoxymethyl group, an ethoxymethyl group,an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethylgroup, an isobutoxymethyl group, a sec-butoxymethyl group, at-butoxymethyl group, a 2-methoxyethyl group, or a 2-methoxy-1-propylgroup is preferable.

Among these phenol derivatives, particularly preferable ones are shownbelow:

In the above formulae, L¹ to L⁸ may be the same or different, and eachindependently represents a hydroxymethyl group, a methoxymethyl group,or an ethoxymethyl group. A phenol derivative having a hydroxymethylgroup can be obtained by reacting the corresponding phenolic compoundhaving no hydroxymethyl group (a compound where L¹ to L⁸ in the aboveformulae are a hydrogen atom) with formaldehyde in the presence of abasic catalyst. In this case, in order to prevent resinification andgelation, the reaction temperature is preferably 60° C. or less.Specifically, it can be synthesized by methods described in JapanesePatent Application Laid-Open Nos. 6-282067 and 7-64285 or the like.

A phenol derivative having an alkoxymethyl group can be obtained byreacting the corresponding phenol derivative having a hydroxymethylgroup with an alcohol in the presence of an acid catalyst. In this case,in order to prevent resinification and gelation, the reactiontemperature is preferably 100° C. or less. Specifically, it can besynthesized by methods described in EP632003A1 or the like.

While the phenol derivative having a hydroxymethyl group and/or analkoxymethyl group thus synthesized is preferable in terms of stabilityupon storage, the phenol derivative having an alkoxymethyl group isparticularly preferable in terms of stability upon storage. The acidcrosslinking agent (G2) may be used alone, or may be used in combinationof two or more kinds.

Other particularly preferable examples of the acid crosslinking agent(G) include a compound having at least one α-hydroxyisopropyl group(acid crosslinking agent (G3)). The compound is not particularly limitedin the structure, as long as it has an α-hydroxyisopropyl group. Ahydrogen atom of a hydroxyl group in the above α-hydroxyisopropyl groupmay be substituted with one or more acid dissociation groups (R—COO—group, R—SO₂— group or the like, wherein R represents a substituentgroup selected from the group consisting of a linear hydrocarbon grouphaving 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branchedalkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbongroup having 6 to 12 carbon atoms). Examples of a compound having theabove α-hydroxyisopropyl group include, but not particularly limited to,one kind or two kinds or more of a substituted or non-substitutedaromatic based compound, a diphenyl compound, a naphthalene compound, afuran compound or the like containing at least one α-hydroxyisopropylgroup. Specific examples thereof include, but not particularly limitedto, a compound represented by the following general formula (9-1)(hereinafter, referred to as “benzene based compound (1)”), a compoundrepresented by the following general formula (9-2) (hereinafter,referred to as “diphenyl based compound (2)”), a compound represented bythe following general formula (9-3) (hereinafter, referred to as“naphthalene based compound (3)”), and a compound represented by thefollowing general formula (9-4) (hereinafter, referred to as “furanbased compound (4)”).

In the above general formulae (9-1) to (9-4), each A² independentlyrepresents an α-hydroxyisopropyl group or a hydrogen atom, and at leastone of A² is an α-hydroxyisopropyl group. In the general formula (9-1),R⁵¹ represents a hydrogen atom, a hydroxyl group, a linear or branchedalkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branchedalkoxycarbonyl group having 2 to 6 carbon atoms. Furthermore, in thegeneral formula (9-2), R⁵² represents a single bond, a linear orbranched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—.Also, in the general formula (9-4), R⁵³ and R⁵⁴ represent a hydrogenatom or a linear or branched alkyl group having 1 to 6 carbon atoms eachindependently.

Specific examples of the benzene based compound (1) include, but notparticularly limited to, α-hydroxyisopropylbenzenes such asα-hydroxyisopropylbenzene, 1,3-bis(α-hydroxyisopropyl)benzene,1,4-bis(α-hydroxyisopropyl)benzene,1,2,4-tris(α-hydroxyisopropyl)benzene, and1,3,5-tris(α-hydroxyisopropyl)benzene; α-hydroxyisopropylphenols such as3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol,3,5-bis(α-hydroxyisopropyl)phenol, and2,4,6-tris(α-hydroxyisopropyl)phenol; α-hydroxyisopropylphenyl alkylketones such as 3-α-hydroxyisopropylphenyl methyl ketone,4-α-hydroxyisopropylphenyl methyl ketone, 4-α-hydroxyisopropylphenylethyl ketone, 4-α-hydroxyisopropylphenyl-n-propyl ketone,4-α-hydroxyisopropylphenyl isopropyl ketone,4-α-hydroxyisopropylphenyl-n-butyl ketone,4-α-hydroxyisopropylphenyl-t-butyl ketone,4-α-hydroxyisopropylphenyl-n-pentyl ketone,3,5-bis(α-hydroxyisopropyl)phenyl methyl ketone,3,5-bis(α-hydroxyisopropyl)phenyl ethyl ketone, and2,4,6-tris(α-hydroxyisopropyl)phenyl methyl ketone; alkyl4-α-hydroxyisopropylbenzoates such as methyl3-αhydroxyisopropylbenzoate, methyl 4-α-hydroxyisopropylbenzoate, ethyl4-α-hydroxyisopropylbenzoate, n-propyl 4-α-hydroxyisopropylbenzoate,isopropyl 4-α-hydroxyisopropylbenzoate, n-butyl4-α-hydroxyisopropylbenzoate, t-butyl 4-α-hydroxyisopropylbenzoate,n-pentyl 4-α-hydroxyisopropylbenzoate, methyl3,5-bis(α-hydroxyisopropyl)benzoate, ethyl3,5-bis(α-hydroxyisopropyl)benzoate, and methyl2,4,6-tris(α-hydroxyisopropyl)benzoate.

Specific examples of the above diphenyl based compound (2) include, butnot particularly limited to, α-hydroxyisopropylbiphenyls such as3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl,3,5-bis(α-hydroxyisopropyl)biphenyl,3,3′-bis(α-hydroxyisopropyl)biphenyl,3,4′-bis(α-hydroxyisopropyl)biphenyl,4,4′-bis(α-hydroxyisopropyl)biphenyl,2,4,6-tris(α-hydroxyisopropyl)biphenyl,3,3′,5-tris(α-hydroxyisopropyl)biphenyl,3,4′,5-tris(α-hydroxyisopropyl)biphenyl,2,3′,4,6,-tetrakis(α-hydroxyisopropyl)biphenyl,2,4,4′,6,-tetrakis(α-hydroxyisopropyl)biphenyl,3,3′,5,5′-tetrakis(α-hydroxyisopropyl)biphenyl,2,3′,4,5′,6-pentakis(α-hydroxyisopropyl)biphenyl, and2,2′,4,4′,6,6′-hexakis(α-hydroxyisopropyl)biphenyl;α-hydroxyisopropyldiphenylalkanes such as3-α-hydroxyisopropyldiphenylmethane,4-α-hydroxyisopropyldiphenylmethane,1-(4-α-hydroxyisopropylphenyl)-2-phenylethane,1-(4-α-hydroxyisopropylphenyl)-2-phenylpropane,2-(4-α-hydroxyisopropylphenyl)-2-phenylpropane,1-(4-α-hydroxyisopropylphenyl)-3-phenylpropane,1-(4-α-hydroxyisopropylphenyl)-4-phenylbutane,1-(4-α-hydroxyisopropylphenyl)-5-phenylpentane,3,5-bis(α-hydroxyisopropyldiphenylmethane,3,3′-bis(α-hydroxyisopropyl)diphenylmethane,3,4′-bis(α-hydroxyisopropyl)diphenylmethane,4,4′-bis(α-hydroxyisopropyl)diphenylmethane,1,2-bis(4-α-hydroxyisopropylphenyl)ethane,1,2-bis(4-α-hydroxypropylphenyl)propane,2,2-bis(4-α-hydroxypropylphenyl)propane,1,3-bis(4-α-hydroxypropylphenyl)propane,2,4,6-tris(α-hydroxyisopropyl)diphenylmethane,3,3′,5-tris(α-hydroxyisopropyl)diphenylmethane,3,4′,5-tris(α-hydroxyisopropyl)diphenylmethane,2,3′,4,6-tetrakis(α-hydroxyisopropyl)diphenylmethane,2,4,4′,6-tetrakis(α-hydroxyisopropyl)diphenylmethane,3,3′,5,5′-tetrakis(α-hydroxyisopropyl)diphenylmethane,2,3′,4,5′,6-pentakis(α-hydroxyisopropyl)diphenylmethane, and2,2′,4,4′,6,6′-hexakis(α-hydroxyisopropyl)diphenylmethane;α-hydroxyisopropyldiphenyl ethers such as 3-α-hydroxyisopropyldiphenylether, 4-α-hydroxyisopropyldiphenyl ether,3,5-bis(α-hydroxyisopropyl)diphenyl ether,3,3′-bis(α-hydroxyisopropyl)diphenyl ether,3,4′-bis(α-hydroxyisopropyl)diphenyl ether,4,4′-bis(α-hydroxyisopropyl)diphenyl ether,2,4,6-tris(α-hydroxyisopropyl)diphenyl ether,3,3′,5-tris(α-hydroxyisopropyl)diphenyl ether,3,4′,5-tris(α-hydroxyisopropyl)diphenyl ether,2,3′,4,6-tetrakis(α-hydroxyisopropyl)diphenyl ether,2,4,4′,6-tetrakis(α-hydroxyisopropyl)diphenyl ether,3,3′,5,5′-tetrakis(α-hydroxyisopropyl)diphenyl ether,2,3′,4,5′,6-pentakis(α-hydroxyisopropyl)diphenyl ether, and2,2′,4,4′,6,6′-hexakis(α-hydroxyisopropyl)diphenyl ether;α-hydroxyisopropyldiphenyl ketones such as 3-α-hydroxyisopropyldiphenylketone, 4-α-hydroxyisopropyldiphenyl ketone,3,5-bis(α-hydroxyisopropyl)diphenyl ketone,3,3′-bis(α-hydroxyisopropyl)diphenyl ketone,3,4′-bis(α-hydroxyisopropyl)diphenyl ketone,4,4′-bis(α-hydroxyisopropyl)diphenyl ketone,2,4,6-tris(α-hydroxyisopropyl)diphenyl ketone,3,3′,5-tris(α-hydroxyisopropyl)diphenyl ketone,3,4′,5-tris(α-hydroxyisopropyl)diphenyl ketone,2,3′,4,6-tetrakis(α-hydroxyisopropyl)diphenyl ketone,2,4,4′,6-tetrakis(α-hydroxyisopropyl)diphenyl ketone,3,3′,5,5′-tetrakis(α-hydroxyisopropyl)diphenyl ketone,2,3′,4,5′,6-pentakis(α-hydroxyisopropyl)diphenyl ketone, and2,2′,4,4′,6,6′-hexakis(α-hydroxyisopropyl)diphenyl ketone; phenylα-hydroxyisopropylbenzoates such as phenyl 3-α-hydroxyisopropylbenzoate,phenyl 4-α-hydroxyisopropylbenzoate, 3-α-hydroxyisopropylphenylbenzoate, 4-α-hydroxyisopropylphenyl benzoate, phenyl3,5-bis(α-hydroxyisopropyl)benzoate, 3-α-hydroxyisopropylphenyl3-α-hydroxyisopropylbenzoate, 4-α-hydroxyisopropylphenyl3-α-hydroxyisopropylbenzoate, 3-α-hydroxyisopropylphenyl4-α-hydroxyisopropylbenzoate, 4-α-hydroxyisopropylphenyl4-α-hydroxyisopropylbenzoate, 3,5-bis(α-hydroxyisopropyl)phenylbenzoate, phenyl 2,4,6-tris(α-hydroxyisopropyl)benzoate,3-α-hydroxyisopropylphenyl 3,5-bis(α-hydroxyisopropyl)benzoate,4-α-hydroxyisopropylphenyl 3,5-bis(α-hydroxyisopropyl)benzoate,3,5-bis(α-hydroxyisopropyl)phenyl 3-α-hydroxyisopropylbenzoate,3,5-bis(α-hydroxyisopropyl)phenyl 4-α-hydroxyisopropylbenzoate,2,4,6-tris(α-hydroxyisopropyl)phenyl benzoate,3-α-hydroxyisopropylphenyl 2,4,6-tris(α-hydroxyisopropyl)benzoate,4-α-hydroxyisopropylphenyl 2,4,6-tris(α-hydroxyisopropyl)benzoate,3,5-bis(α-hydroxyisopropyl) phenyl 3,5-bis(α-hydroxyisopropyl)benzoate,2,4,6-tris(α-hydroxyisopropyl)phenyl 3-α-hydroxyisopropylbenzoate,2,4,6-tris(α-hydroxyisopropyl)phenyl 4-α-hydroxyisopropylbenzoate,3,5-bis(α-hydroxyisopropyl)phenyl2,4,6-tris(α-hydroxyisopropyl)benzoate,2,4,6-tris(α-hydroxyisopropyl)phenyl3,5-bis(α-hydroxyisopropyl)benzoate, and2,4,6-tris(α-hydroxyisopropyl)phenyl2,4,6-tris(α-hydroxyisopropyl)benzoate.

Furthermore, specific examples of the above naphthalene based compound(3) include, but not particularly limited to,1-(α-hydroxyisopropyl)naphthalene, 2-(α-hydroxyisopropyl)naphthalene,1,3-bis(α-hydroxyisopropyl)naphthalene,1,4-bis(α-hydroxyisopropyl)naphthalene,1,5-bis(α-hydroxyisopropyl)naphthalene,1,6-bis(α-hydroxyisopropyl)naphthalene,1,7-bis(α-hydroxyisopropyl)naphthalene,2,6-bis(α-hydroxyisopropyl)naphthalene,2,7-bis(α-hydroxyisopropyl)naphthalene, 1,3,5-tris(α-hydroxyisopropyl)naphthalene, 1,3,6-tris(α-hydroxyisopropyl)naphthalene,1,3,7-tris(α-hydroxyisopropyl)naphthalene,1,4,6-tris(α-hydroxyisopropyl)naphthalene,1,4,7-tris(α-hydroxyisopropyl)naphthalene, and1,3,5,7-tetrakis(α-hydroxyisopropyl) naphthalene.

Specific examples of the above furan based compound (4) include, but notparticularly limited to, 3-(α-hydroxyisopropyl)furan,2-methyl-3-(α-hydroxyisopropyl)furan,2-methyl-4-(α-hydroxyisopropyl)furan,2-ethyl-4-(α-hydroxyisopropyl)furan,2-n-propyl-4-(α-hydroxyisopropyl)furan,2-isopropyl-4-(α-hydroxyisopropyl)furan,2-n-butyl-4-(α-hydroxyisopropyl)furan,2-t-butyl-4-(α-hydroxyisopropyl)furan,2-n-pentyl-4-(α-hydroxyisopropyl)furan,2,5-dimethyl-3-(α-hydroxyisopropyl)furan,2,5-diethyl-3-(α-hydroxyisopropyl)furan,3,4-bis(α-hydroxyisopropyl)furan,2,5-dimethyl-3,4-bis(α-hydroxyisopropyl)furan, and2,5-diethyl-3,4-bis(α-hydroxyisopropyl)furan.

As the above acid crosslinking agent (G3), a compound having two or morefree α-hydroxyisopropyl groups is preferable; the above benzene basedcompound (1) having two or more α-hydroxyisopropyl groups, the abovediphenyl based compound (2) having two or more α-hydroxyisopropylgroups, and the above naphthalene based compound (3) having two or moreα-hydroxyisopropyl groups are more preferable; andα-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groupsand the above naphthalene based compound (3) having two or moreα-hydroxyisopropyl groups are particularly preferable.

The above acid crosslinking agent (G3) can normally be obtained by amethod for reacting an acetyl group-containing compound such as1,3-diacetylbenzene with Grignard reagent such as CH₃MgBr to methylateand then hydrolyzing, or a method for oxidizing an isopropylgroup-containing compound such as 1,3-diisopropylbenzene with oxygen orthe like to produce a peroxide and then reducing.

The content of the acid crosslinking agent (G) in theradiation-sensitive composition of the present embodiment is preferably0.5 to 49% by weight of the total weight of the solid component, morepreferably 0.5 to 40% by weight, still more preferably 1 to 30% byweight, and particularly preferably 2 to 20% by weight. When the contentof the above acid crosslinking agent (G) in the radiation-sensitivecomposition of the present embodiment is 0.5% by weight or more, theinhibiting effect of the solubility of a resist film in an alkalinedeveloping solution can be improved, and a decrease in the filmremaining rate, and occurrence of swelling and meandering of a patterncan be inhibited, which is preferable. On the other hand, when thecontent of the above acid crosslinking agent (G) is 50% by weight orless, a decrease in heat resistance as a resist can be inhibited, whichis preferable.

The blending ratio of at least one kind of compound selected from theabove acid crosslinking agent (G1), acid crosslinking agent (G2), andacid crosslinking agent (G3) in the above acid crosslinking agent (G) isalso not particularly limited, and can be within various rangesaccording to the kind of substrates or the like used upon forming aresist pattern.

In all acid crosslinking agent components, the contents of the abovealkoxymethylated melamine compound and/or the compounds represented by(9-1) to (9-3) are 50 to 99% by weight, preferably 60 to 99% by weight,more preferably 70 to 98% by weight, and still more preferably 80 to 97%by weight. By having the contents of the alkoxymethylated melaminecompound and/or the compounds represented by (9-1) to (9-3) of 50% byweight or more of all acid crosslinking agent components, the resolutionof the radiation-sensitive composition of the present embodiment can beimproved, which is preferable. By having the compounds of 99% by weightor less, the pattern cross section is likely to have a rectangularshape, which is preferable.

The radiation-sensitive composition of the present embodiment mayfurther contain an acid diffusion controlling agent (E). The aciddiffusion controlling agent (E) has a function of controlling diffusionof an acid generated from an acid generating agent by radiationirradiation in a resist film to inhibit any unpreferable chemicalreaction in an unexposed region or the like. When theradiation-sensitive composition of the present embodiment contains suchan acid diffusion controlling agent (E), the storage stability of theradiation-sensitive composition is improved. Also, along with theimprovement of the resolution, the line width change of a resist patterndue to variation in the post exposure delay time before radiationirradiation and the post exposure delay time after radiation irradiationcan be inhibited, and the composition has extremely excellent processstability. Examples of such an acid diffusion controlling agent (E)include, but not particularly limited to, a radiation degradable basiccompound such as a nitrogen atom-containing basic compound, a basicsulfonium compound, and a basic iodonium compound. The acid diffusioncontrolling agent (E) can be used alone or in combination of two or morekinds.

Examples of the above acid diffusion controlling agent (E) include, butnot particularly limited to, a nitrogen-containing organic compound, anda basic compound degradable by exposure. Examples of the abovenitrogen-containing organic compound include a compound represented bythe following general formula (10):

(hereinafter, referred to as a “nitrogen-containing compound (I)”), adiamino compound having two nitrogen atoms within the same molecule(hereinafter, referred to as a “nitrogen-containing compound (II)”), apolyamino compound or polymer having three or more nitrogen atoms(hereinafter, referred to as a “nitrogen-containing compound (III)”), anamide group-containing compound, a urea compound, and anitrogen-containing heterocyclic compound. The acid diffusioncontrolling agent (E) may be used alone as one kind or may be used incombination of two or more kinds.

In the above general formula (10), R⁶¹, R⁶², and R⁶³ represent ahydrogen atom, a linear, branched or cyclic alkyl group, an aryl group,or an aralkyl group each independently. The above alkyl group, arylgroup, or aralkyl group may be non-substituted or may be substitutedwith a hydroxyl group or the like. Herein, examples of the above linear,branched or cyclic alkyl group include the one having 1 to 15, andpreferably 1 to 10 carbon atoms. Specific examples thereof include, butnot particularly limited to, a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group, asec-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group,an n-hexyl group, a texyl group, an n-heptyl group, an n-octyl group, ann-ethylhexyl group, an n-nonyl group, and an n-decyl group. Examples ofthe above aryl group include the one having 6 to 12 carbon atoms.Specific examples thereof include, but not particularly limited to, aphenyl group, a tolyl group, a xylyl group, a cumenyl group, and a1-naphthyl group. Furthermore, examples of the above aralkyl groupinclude, but not particularly limited to, the one having 7 to 19, andpreferably 7 to 13 carbon atoms. Specific examples thereof include abenzyl group, an α-methylbenzyl group, a phenethyl group, and anaphthylmethyl group.

Specific examples of the above nitrogen-containing compound (I) include,but not particularly limited to, mono(cyclo)alkylamines such asn-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine,n-dodecylamine, and cyclohexylamine; di(cyclo)alkylamines such asdi-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine,di-n-octylamine, di-n-nonylamine, di-n-decylamine,methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, anddicyclohexylamine; tri(cyclo)alkylamines such as triethylamine,tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine,tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine,tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine,dicyclohexylmethylamine, and tricyclohexylamine; alkanolamines such asmonoethanolamine, diethanolamine, and triethanolamine; and aromaticamines such as aniline, N-methylaniline, N,N-dimethylaniline,2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline,diphenylamine, triphenylamine, and 1-naphthylamine.

Specific examples of the above nitrogen-containing compound (II)include, but not particularly limited to, ethylenediamine,N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,tetramethylenediamine, hexamethylenediamine,4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether,4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine,2,2-bis(4-aminophenyl)propane,2-(3-aminophenyl)-2-(4-aminophenyl)propane,2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane,2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane,1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, and1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene.

Specific examples of the above nitrogen-containing compound (III)include, but not particularly limited to, polymers of polyethyleneimine,polyarylamine, and N-(2-dimethylaminoethyl)acrylamide.

Specific examples of the above amide group-containing compound include,but not particularly limited to, formamide, N-methylformamide,N,N-dimethylformamide, acetamide, N-methylacetamide,N,N-dimethylacetamide, propioneamide, benzamide, pyrrolidone, andN-methylpyrrolidone.

Specific examples of the above urea compound include, but notparticularly limited to, urea, methylurea, 1,1-dimethylurea,1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, andtri-n-butylthiourea.

Specific examples of the above nitrogen-containing heterocyclic compoundinclude, but not particularly limited to, imidazoles such as imidazole,benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and2-phenylbenzimidazole; pyridines such as pyridine, 2-methylpyridine,4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine,4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid,amide nicotinate, quinoline, 8-oxyquinoline, and acridine; and pyrazine,pyrazole, pyridazine, quinozaline, purine, pyrrolidine, piperidine,morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, and1,4-diazabicyclo[2.2.2]octane.

Examples of the above radiation degradable basic compound include, butnot particularly limited to, a sulfonium compound represented by thefollowing general formula (11-1):

and an iodonium compound represented by the following general formula(11-2):

In the above general formulae (11-1) and (11-2), R⁷¹, R⁷², R⁷³, R⁷⁴, andR⁷⁵ represent a hydrogen atom, an alkyl group having 1 to 6 carbonatoms, an alkoxyl group having 1 to 6 carbon atoms, a hydroxyl group, ora halogen atom each independently. Z⁻ represents HO⁻, R—COO⁻ (Rrepresents an alkyl group having 1 to 6 carbon atoms, an aryl grouphaving 6 to 11 carbon atoms, or an alkaryl group having 7 to 12 carbonatoms), or an anion represented by the following general formula (11-3):

Specific examples of the above radiation degradable basic compoundinclude, but not particularly limited to, triphenylsulfonium hydroxide,triphenylsulfonium acetate, triphenylsulfonium salicylate,diphenyl-4-hydroxyphenylsulfonium hydroxide,diphenyl-4-hydroxyphenylsulfonium acetate,diphenyl-4-hydroxyphenylsulfonium salicylate,bis(4-t-butylphenyl)iodonium hydroxide, bis(4-t-butylphenyl)iodoniumacetate, bis(4-t-butylphenyl)iodonium hydroxide,bis(4-t-butylphenyl)iodonium acetate, bis(4-t-butylphenyl)iodoniumsalicylate, 4-t-butylphenyl-4-hydroxyphenyliodonium hydroxide,4-t-butylphenyl-4-hydroxyphenyliodonium acetate, and4-t-butylphenyl-4-hydroxyphenyliodonium salicylate.

The content of the acid diffusion controlling agent (E) in theradiation-sensitive composition of the present embodiment is preferably0.001 to 49% by weight of the total weight of the solid component, morepreferably 0.01 to 10% by weight, still more preferably 0.01 to 5% byweight, and particularly preferably 0.01 to 3% by weight. When thecontent of the acid diffusion controlling agent (E) in theradiation-sensitive composition of the present embodiment is within theabove range, a decrease in resolution, and deterioration of the patternshape and the dimension fidelity or the like can be prevented. Moreover,even though the post exposure delay time from electron beam irradiationto heating after radiation irradiation becomes longer, the shape of thepattern upper layer portion is not deteriorated. When the content of theacid diffusion controlling agent (E) in the radiation-sensitivecomposition of the present embodiment is 10% by weight or less, adecrease in sensitivity, and developability of the unexposed portion orthe like can be prevented. By using such an acid diffusion controllingagent (E), the storage stability of a radiation-sensitive compositionimproves, also along with improvement of the resolution, the line widthchange of a resist pattern due to variation in the post exposure delaytime before radiation irradiation and the post exposure delay time afterradiation irradiation can be inhibited, and the composition hasextremely excellent process stability.

To the radiation-sensitive composition of the present embodiment, withinthe range of not inhibiting the purpose of the present invention, ifrequired, as the other component (F), one kind or two kinds or more ofvarious additive agents such as a dissolution promoting agent, adissolution controlling agent, a sensitizing agent, a surfactant and anorganic carboxylic acid or an oxo acid of phosphor, or derivativethereof can be added.

(1) Dissolution Promoting Agent

A dissolution promoting agent is a component having a function ofincreasing the solubility of a cyclic compound such as described abovein a developing solution to moderately increase the dissolution rate ofthe cyclic compound upon developing, when the solubility of the cycliccompound is too low. The low molecular weight dissolution promotingagent can be used, within the range of not deteriorating the effect ofthe present invention. Examples of the above dissolution promoting agentinclude, but not particularly limited to, a low molecular weightphenolic compound. Specific examples thereof include bisphenols andtris(hydroxyphenyl)methane. These dissolution promoting agents can beused alone or in mixture of two or more kinds. The content of thedissolution promoting agent in the radiation-sensitive composition ofthe present embodiment, which is arbitrarily adjusted according to thekind of cyclic compound to be used, is preferably 0 to 49% by weight ofthe total weight of the solid component, more preferably 0 to 5% byweight, still more preferably 0 to 1% by weight, and particularlypreferably 0% by weight.

(2) Dissolution Controlling Agent

The dissolution controlling agent is a component having a function ofcontrolling the solubility of the cyclic compound such as describedabove in a developing solution to moderately decrease the dissolutionrate upon developing, when the solubility of the cyclic compound is toohigh. As such a dissolution controlling agent, the one which does notchemically change in steps such as calcination of resist coating,radiation irradiation, and development is preferable.

Examples of the dissolution controlling agent include, but notparticularly limited to, aromatic hydrocarbons such as phenanthrene,anthracene, and acenaphthene; ketones such as acetophenone,benzophenone, and phenyl naphtyl ketone; and sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Thesedissolution controlling agents can be used alone or in two or morekinds.

The content of the dissolution controlling agent in theradiation-sensitive composition of the present embodiment, which isarbitrarily adjusted according to the kind of cyclic compound to beused, is preferably 0 to 49% by weight of the total weight of the solidcomponent, more preferably 0 to 5% by weight, still more preferably 0 to1% by weight, and particularly preferably 0% by weight.

(3) Sensitizing Agent

The sensitizing agent is a component having a function of absorbingirradiated radiation energy, transmitting the energy to the acidgenerating agent (C), and thereby increasing the acid production amount,and improving the apparent sensitivity of a resist. Examples of such asensitizing agent include, but not particularly limited to,benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. Thesesensitizing agents can be used alone or in two or more kinds. Thecontent of the sensitizing agent in the radiation-sensitive compositionof the present embodiment, which is arbitrarily adjusted according tothe kind of cyclic compound to be used, is preferably 0 to 49% by weightof the total weight of the solid component, more preferably 0 to 5% byweight, still more preferably 0 to 1% by weight, and particularlypreferably 0% by weight.

(4) Surfactant

The surfactant is a component having a function of improving coatabilityand striation of the radiation-sensitive composition of the presentembodiment, and developability of a resist or the like. Such asurfactant may be any of anionic, cationic, nonionic or amphoteric. Apreferable surfactant is a nonionic surfactant. The nonionic surfactanthas a good affinity with a solvent used in production ofradiation-sensitive compositions and more effects. Examples of thenonionic surfactant include, but not particularly limited to, apolyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenylethers, and higher fatty acid diesters of polyethylene glycol. Examplesof commercially available products include, but not particularly limitedto, hereinafter by trade name, EFTOP (manufactured by Jemco Inc.),MEGAFAC (manufactured by DIC Corporation), Fluorad (manufactured bySumitomo 3M Limited), AsahiGuard, Surflon (hereinbefore, manufactured byAsahi Glass Co., Ltd.), Pepole (manufactured by Toho Chemical IndustryCo., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), andPolyflow (manufactured by Kyoeisha Chemical Co., Ltd.). The content ofthe surfactant in the radiation-sensitive composition of the presentembodiment, which is arbitrarily adjusted according to the kind ofcyclic compound to be used, is preferably 0 to 49% by weight of thetotal weight of the solid component, more preferably 0 to 5% by weight,still more preferably 0 to 1% by weight, and particularly preferably 0%by weight.

(5) Organic Carboxylic Acid or Oxo Acid of Phosphor or DerivativeThereof

For the purpose of prevention of sensitivity deterioration orimprovement of a resist pattern shape and post exposure delay stabilityor the like, and as an additional optional component, theradiation-sensitive composition of the present embodiment can contain anorganic carboxylic acid or an oxo acid of phosphor or derivativethereof. The composition can be used in combination with the aciddiffusion controlling agent, or may be used alone. As the organiccarboxylic acid, for example, malonic acid, citric acid, malic acid,succinic acid, benzoic acid, and salicylic acid, or the like arepreferable, but not particularly limited to these. Examples of the oxoacid of phosphor or derivative thereof include, but not particularlylimited to, phosphoric acid or derivative thereof such as esterincluding phosphoric acid, di-n-butyl ester phosphate, and diphenylester phosphate; phosphonic acid or derivative thereof such as esterincluding phosphonic acid, dimethyl ester phosphonate, di-n-butyl esterphosphonate, phenylphosphonic acid, diphenyl ester phosphonate, anddibenzyl ester phosphonate; and phosphinic acid and derivative thereofsuch as ester including phosphinic acid and phenylphosphinic acid. Amongthem, phosphonic acid is particularly preferable.

The organic carboxylic acid or the oxo acid of phosphor or derivativethereof can be used alone or in combination of two or more kinds. Thecontent of the organic carboxylic acid or the oxo acid of phosphor orderivative thereof in the radiation-sensitive composition of the presentembodiment, which is arbitrarily adjusted according to the kind ofcyclic compound to be used, is preferably 0 to 49% by weight of thetotal weight of the solid component, more preferably 0 to 5% by weight,still more preferably 0 to 1% by weight, and particularly preferably 0%by weight.

(6) Other Additive Agent Than the Above Dissolution Controlling Agent,Sensitizing Agent, Surfactant, and Organic Carboxylic Acid or Oxo Acidof Phosphor or Derivative Thereof

Furthermore, the radiation-sensitive composition of the presentembodiment can contain one kind or two kinds or more of additive agentsother than the above dissolution controlling agent, sensitizing agent,and surfactant, within the range of not inhibiting the purpose of thepresent invention, if required. Examples of such an additive agentinclude, but not particularly limited to, a dye, a pigment, and anadhesion aid. For example, the radiation-sensitive composition of thepresent embodiment contains the dye or the pigment, and thereby a latentimage of the exposed portion can be visualized and influence of halationupon exposure can be alleviated, which is preferable. Theradiation-sensitive composition of the present embodiment contains theadhesion aid, and thereby adhesiveness to a substrate can be improved,which is preferable. Furthermore, examples of other additive agentinclude a halation preventing agent, a storage stabilizing agent, adefoaming agent, and a shape improving agent. Specific examples thereofinclude 4-hydroxy-4′-methylchalkone.

The total content of the above optional component (F) in theradiation-sensitive composition of the present embodiment is preferably0 to 49% by weight of the total weight of the solid component, morepreferably 0 to 5% by weight, still more preferably 0 to 1% by weight,and particularly preferably 0% by weight.

In the radiation-sensitive composition of the present embodiment, thecontent ratio of each component (cyclic compound/acid generating agent(C)/acid crosslinking agent (G)/acid diffusion controlling agent(E)/optional component (F)) is preferably 50 to 99.4/0.001 to 49/0.5 to49/0.001 to 49/0 to 49, in % by weight based on the solid component,more preferably 55 to 90/1 to 40/0.5 to 40/0.01 to 10/0 to 5, still morepreferably 60 to 80/3 to 30/1 to 30/0.01 to 5/0 to 1, and particularlypreferably 60 to 70/10 to 25/2 to 20/0.01 to 3/0. The content ratio ofeach component is selected from each range so that the summation thereofis 100% by weight. In the content ratio of each component, theradiation-sensitive composition of the present embodiment has excellentperformances such as sensitivity, resolution, and developability.

The radiation-sensitive composition of the present embodiment istypically prepared by dissolving each component in a solvent upon useinto a homogenous solution, and then if required, filtering through afilter or the like with a pore diameter of about 0.2 μm, for example.

Examples of the solvent used in the preparation of theradiation-sensitive composition of the present embodiment include, butnot particularly limited to, ethylene glycol monoalkyl ether acetatessuch as ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate,and ethylene glycol mono-n-butyl ether acetate; ethylene glycolmonoalkyl ethers such as ethylene glycol monomethyl ether and ethyleneglycol monoethyl ether; propylene glycol monoalkyl ether acetates suchas propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol mono-n-propyl ether acetate, andpropylene glycol mono-n-butyl ether acetate; propylene glycol monoalkylethers such as propylene glycol monomethyl ether and propylene glycolmonoethyl ether; ester lactates such as methyl lactate, ethyl lactate,n-propyl lactate, n-butyl lactate, and n-amyl lactate; aliphaticcarboxylic acid esters such as methyl acetate, ethyl acetate, n-propylacetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methylpropionate, and ethyl propionate; other esters such as methyl3-methoxypropionate, ethyl 3-methoxypropionate, methyl3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl3-methoxy-2-methylpropionate, 3-methoxybutylacetate,3-methyl-3-methoxybutylacetate, butyl 3-methoxy-3-methylpropionate,butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate,and ethyl pyruvate; aromatic hydrocarbon atoms such as toluene andxylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone,cyclopentanone, and cyclohexanone; amides such as N,N-dimethylformamide,N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; andlactones such as γ-lactone. These solvents can be used alone or incombination of two or more kinds.

The radiation-sensitive composition of the present embodiment cancontain a resin within the range of not inhibiting the purpose of thepresent invention. Examples of the resin include, but not particularlylimited to, a novolac resin, polyvinyl phenols, polyacrylic acid,polyvinyl alcohol, a styrene-maleic anhydride resin, and a polymercontaining acrylic acid, vinyl alcohol or vinylphenol as a monomericunit, or derivative thereof. The content of the resin in theradiation-sensitive composition of the present embodiment, which isarbitrarily adjusted according to the kind of cyclic compound describedabove to be used, is preferably 30 parts by weight or less per 100 partsby weight of the above cyclic compound, more preferably 10 parts byweight or less, still more preferably 5 parts by weight or less, andparticularly preferably 0 part by weight.

(Resist Pattern Formation Method)

A resist pattern formation method of the present embodiment includes thesteps of forming a resist film by coating a substrate with the aboveradiation-sensitive composition, exposing the resist film, anddeveloping the exposed resist film to form a resist pattern. The resistpattern of the present embodiment can also be formed as an upper layerresist in a multilayer process.

In order to form a resist pattern, a resist film is formed by coating aconventionally publically known substrate with the radiation-sensitivecomposition using a coating means such as spin coating, flow castingcoating, and roll coating. The conventionally publically known substrateis not particularly limited. For example, a substrate for electroniccomponents, and the one having a predetermined wiring pattern formedthereon, or the like can be exemplified. More specific examples include,but not particularly limited to, a substrate made of a metal such as asilicon wafer, copper, chromium, iron and aluminum, and a glasssubstrate. Examples of a wiring pattern material include, but notparticularly limited to, copper, aluminum, nickel, and gold. Also ifrequired, the substrate may be a substrate having an inorganic and/ororganic film provided thereon. Examples of the inorganic film include,but not particularly limited to, an inorganic antireflection film(inorganic BARC). Examples of the organic film include, but notparticularly limited to, an organic antireflection film (organic BARC).Surface treatment with hexamethylene disilazane or the like may beconducted.

Then, the coated substrate is heated if required. The heatingtemperatures vary according to the blending composition of theradiation-sensitive composition, or the like, but are preferably 20 to250° C., and more preferably 20 to 150° C. By heating, the adhesivenessof a radiation-sensitive composition (resist) to a substrate mayimprove, which is preferable. Then, the resist film is exposed to adesired pattern by any radiation selected from the group consisting ofvisible light, ultraviolet, excimer laser, electron beam, extremeultraviolet (EUV), X-ray, and ion beam. The exposure conditions or thelike are arbitrarily selected according to the compounding compositionof the radiation-sensitive composition, or the like. In the resistpattern formation method of the present embodiment, in order to stablyform a fine pattern with a high degree of accuracy in exposure, theresist film is preferably heated after radiation irradiation. Theheating temperatures vary according to the compounding composition ofthe radiation-sensitive composition, or the like, but are preferably 20to 250° C., and more preferably 20 to 150° C.

Next, by developing the exposed resist film in a developing solution(development step), a predetermined resist pattern is formed. Thedeveloping solution is a solvent having a solubility parameter (SPvalue) close to that of the cyclic compound described above to be usedis preferably selected. For example, a polar solvent such as aketone-based solvent, an ester-based solvent, an alcohol-based solvent,an amide-based solvent, and an ether-based solvent; and ahydrocarbon-based solvent, or an alkaline aqueous solution can be used.

Examples of the ketone-based solvent include, but not particularlylimited to, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone,4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone,methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol,acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, andpropylene carbonate.

Examples of the ester-based solvent include, but not particularlylimited to, methyl acetate, butyl acetate, ethyl acetate, isopropylacetate, amyl acetate, propylene glycol monomethyl ether acetate,ethylene glycol monoethyl ether acetate, diethylene glycol monobutylether acetate, diethylene glycol monoethyl ether acetate,ethyl-3-ethoxypropionate, 3-methoxybutyl acetate,3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butylformate, propyl formate, ethyl lactate, butyl lactate, and propyllactate.

Examples of the alcohol-based solvent include, but not particularlylimited to, an alcohol such as methyl alcohol, ethyl alcohol, n-propylalcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butylalcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol,4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, and n-decanol; aglycol-based solvent such as ethylene glycol, diethylene glycol, andtriethylene glycol; and a glycol ether-based solvent such as ethyleneglycol monomethyl ether, propylene glycol monomethyl ether, ethyleneglycol monoethyl ether, propylene glycol monoethyl ether, diethyleneglycol monomethyl ether, triethylene glycol monoethyl ether, andmethoxymethyl butanol.

Examples of the ether-based solvent include, but not particularlylimited to, dioxane and tetrahydrofuran in addition to the above glycolether-based solvents.

Examples of the amide-based solvent which can be used include, but notparticularly limited to, N-methyl-2-pyrrolidone, N,N-dimethylacetamide,N,N-dimethylformamide, phosphoric hexamethyltriamide, and1,3-dimethyl-2-imidazolidinone.

Examples of the hydrocarbon-based solvent include, but not particularlylimited to, an aromatic hydrocarbon-based solvent such as toluene andxylene; and an aliphatic hydrocarbon-based solvent such as pentane,hexane, octane, and decane.

A plurality of these solvents may be mixed, or the solvent may be usedby mixing the solvent with a solvent other than those described above orwater within the range having performance. However, in order tosufficiently exhibit the effect of the present invention, the watercontent ratio based on the whole developing solution is less than 70% bymass, preferably less than 50% by mass, more preferably less than 30% bymass, and still more preferably less than 10% by mass. Particularlypreferably, the developing solution is substantially moisture free. Thatis, the content of the organic solvent in the developing solution is 30%by mass or more and 100% by mass or less based on the total amount ofthe developing solution, preferably 50% by mass or more and 100% by massor less, more preferably 70% by mass or more and 100% by mass or less,still more preferably 90% by mass or more and 100% by mass or less, andparticularly preferably 95% by mass or more and 100% by mass or less.

Examples of the alkaline aqueous solution include, but not particularlylimited to, an alkaline compound such as mono-, di- or tri-alkylamines,mono-, di- or tri-alkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline.

Particularly, the developing solution containing at least one kind ofsolvent selected from a ketone-based solvent, an ester-based solvent, analcohol-based solvent, an amide-based solvent, and an ether-basedsolvent improves resist performance such as resolution and roughness ofthe resist pattern, which is preferable.

The vapor pressure of the developing solution is preferably 5 kPa orless at 20° C., more preferably 3 kPa or less, and particularlypreferably 2 kPa or less. The evaporation of the developing solution onthe substrate or in a developing cup is inhibited by setting the vaporpressure of the developing solution to 5 kPa or less, to improvetemperature uniformity within a wafer surface, thereby resulting inimprovement in size uniformity within the wafer surface.

Specific examples of the solvent for the developing solution having avapor pressure of 5 kPa or less at 20° C. include, but not particularlylimited to, a ketone-based solvent such as 1-octanone, 2-octanone,1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone,cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutylketone; an ester-based solvent such as butyl acetate, amyl acetate,propylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate, diethyleneglycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxy butyl acetate, butyl formate, propylformate, ethyl lactate, butyl lactate, and propyl lactate; analcohol-based solvent such as n-propyl alcohol, isopropyl alcohol,n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutylalcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octylalcohol, and n-decanol; a glycol-based solvent such as ethylene glycol,diethylene glycol, and triethylene glycol; a glycol ether-based solventsuch as ethylene glycol monomethyl ether, propylene glycol monomethylether, ethylene glycol monoethyl ether, propylene glycol monoethylether, diethylene glycol monomethyl ether, triethylene glycol monoethylether, and methoxymethyl butanol; an ether-based solvent such astetrahydrofuran; an amide-based solvent such as N-methyl-2-pyrrolidone,N,N-dimethylacetamide, and N,N-dimethylformamide; an aromatichydrocarbon-based solvent such as toluene and xylene; and an aliphatichydrocarbon-based solvent such as octane and decane.

Specific examples of the developing solution having a vapor pressure of2 kPa or less which is a particularly preferable range include, but notparticularly limited to, a ketone-based solvent such as 1-octanone,2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, and phenylacetone; anester-based solvent such as butyl acetate, amyl acetate, propyleneglycol monomethyl ether acetate, ethylene glycol monoethyl etheracetate, diethylene glycol monobutyl ether acetate, diethylene glycolmonoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxy butylacetate, 3-methyl-3-methoxy butyl acetate, ethyl lactate, butyl lactate,and propyl lactate; an alcohol-based solvent such as n-butyl alcohol,sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexylalcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, andn-decanol; a glycol-based solvent such as ethylene glycol, diethyleneglycol, and triethylene glycol; a glycol ether-based solvent such asethylene glycol monomethyl ether, propylene glycol monomethyl ether,ethylene glycol monoethyl ether, propylene glycol monoethyl ether,diethylene glycol monomethyl ether, triethylene glycol monoethyl ether,and methoxymethyl butanol; an amide-based solvent such asN-methyl-2-pyrrolidone, N,N-dimethylacetamide, andN,N-dimethylformamide; an aromatic hydrocarbon-based solvent such asxylene; and an aliphatic hydrocarbon-based solvent such as octane anddecane.

To the developing solution, a surfactant can be added in an appropriateamount, if required.

The surfactant is not particularly limited but, for example, an ionic ornonionic fluorine-based and/or silicon-based surfactant can be used.Examples of the fluorine-based and/or silicon-based surfactant includethe surfactants described in Japanese Patent Application Laid-Open Nos.62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834,9-54432, and 9-5988, and U.S. Pat. Nos. 5,405,720, 5,360,692, 5,529,881,5,296,330, 5,436,098, 5,576,143, 5,294,511, and 5,824,451. Thesurfactant is preferably a nonionic surfactant. The nonionic surfactantis not particularly limited, but a fluorine-based surfactant or asilicon-based surfactant is more preferably used, for example.

The amount of the surfactant used is usually 0.001 to 5% by mass basedon the total amount of the developing solution, preferably 0.005 to 2%by mass, and more preferably 0.01 to 0.5% by mass.

The development method is not particularly limited. For example, amethod for dipping a substrate in a bath filled with a developingsolution for a fixed time (dipping method), a method for raising adeveloping solution on a substrate surface by the effect of a surfacetension and keeping it still for a fixed time, thereby conducting thedevelopment (puddle method), a method for spraying a developing solutionon a substrate surface (spraying method), and a method for continuouslyejecting a developing solution on a substrate rotating at a constantspeed while scanning a developing solution ejecting nozzle at a constantrate (dynamic dispense method), or the like may be applied. The time forconducting the pattern development is not particularly limited, but ispreferably 10 seconds to 90 seconds.

After the step of conducting development, a step of stopping thedevelopment by the replacement with another solvent may be practiced inthe resist pattern formation method of the present embodiment.

Furthermore, the resist pattern formation method of the presentembodiment preferably includes a step (rinsing step) of rinsing theresist film with a rinsing solution containing an organic solvent afterthe development step.

The rinsing solution used in the rinsing step after development step isnot particularly limited as long as the rinsing solution does notdissolve the resist pattern cured by crosslinking. A solution containinga general organic solvent or water may be used as the rinsing solution.As the rinsing solution, a rinsing solution containing at least one kindof organic solvent selected from a hydrocarbon-based solvent, aketone-based solvent, an ester-based solvent, an alcohol-based solvent,an amide-based solvent, and an ether-based solvent is preferably used,but not particularly limited to these. More preferably, afterdevelopment step, a step of rinsing the film by using a rinsing solutioncontaining at least one kind of organic solvent selected from the groupconsisting of a ketone-based solvent, an ester-based solvent, analcohol-based solvent and an amide-based solvent is conducted. Stillmore preferably, after development step, a step of rinsing the film byusing a rinsing solution containing an alcohol-based solvent or anester-based solvent is conducted. Yet still more preferably, afterdevelopment step, a step of rinsing the film by using a rinsing solutioncontaining a monohydric alcohol is conducted. Particularly preferably,after development step, a step of rinsing the film by using a rinsingsolution containing a monohydric alcohol having 5 or more carbon atomsis conducted. The time for rinsing the pattern is not particularlylimited, but is preferably 10 seconds to 90 seconds.

Herein, examples of the monohydric alcohol used in the rinsing stepafter development step include, but not particularly limited to, alinear, branched or cyclic monohydric alcohol. Specifically, 1-butanol,2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol,2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol,2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol,3-octanol, and 4-octanol or the like can be used. As the particularlypreferable monohydric alcohol having 5 or more carbon atoms, 1-hexanol,2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol orthe like can be used, but not particularly limited to these.

A plurality of these components may be mixed, or the component may beused by mixing the component with an organic solvent other than thosedescribed above.

The water content ratio in the rinsing solution is preferably 10% bymass or less, more preferably 5% by mass or less, and particularlypreferably 3% by mass or less. By setting the water content ratio in therinsing solution to 10% by mass or less, better developmentcharacteristics can be obtained.

The vapor pressure at 20° C. of the rinsing solution used afterdevelopment step is preferably 0.05 kPa or more and 5 kPa or less, morepreferably 0.1 kPa or more and 5 kPa or less, and further preferably0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of therinsing solution to 0.05 kPa or more and 5 kPa or less, the temperatureuniformity in the wafer surface is enhanced and moreover, swelling dueto permeation of the rinsing solution is further inhibited. As a result,the dimensional uniformity in the wafer surface is further improved.

The rinsing solution may also be used after adding an appropriate amountof a surfactant to the rinsing solution.

In the rinsing step, the wafer after development step is preferablyrinsed using the organic solvent-containing rinsing solution. The methodfor rinsing treatment is not particularly limited. However, for example,a method for continuously ejecting a rinsing solution on a substratespinning at a constant speed (spin coating method), a method for dippinga substrate in a bath filled with a rinsing solution for a fixed time(dipping method), and a method for spraying a rinsing solution on asubstrate surface (spraying method), or the like can be applied. Aboveall, it is preferable to conduct the rinsing treatment by the spincoating method and after the rinsing, spin the substrate at a rotationalspeed of 2,000 rpm to 4,000 rpm, to remove the rinsing solution from thesubstrate surface.

After forming the resist pattern, a pattern wiring substrate is obtainedby etching. Etching can be conducted by a publicly known method such asdry etching using plasma gas, and wet etching with an alkaline solution,a cupric chloride solution, and a ferric chloride solution or the like.

After forming the resist pattern, plating can also be conducted.Examples of the above plating method include, but not particularlylimited to, copper plating, solder plating, nickel plating, and goldplating.

The remaining resist pattern after etching can be peeled by an organicsolvent. Examples of the above organic solvent include, but notparticularly limited to, PGMEA (propylene glycol monomethyl etheracetate), PGME (propylene glycol monomethyl ether), and EL (ethyllactate). Examples of the above peeling method include, but notparticularly limited to, a dipping method and a spraying method. Awiring substrate having a resist pattern formed thereon may be amultilayer wiring substrate, and may have a small diameter through hole.

In the present embodiment, the wiring substrate can also be formed by amethod for forming a resist pattern, then depositing a metal in vacuum,and subsequently dissolving the resist pattern in a solution, i.e., aliftoff method.

EXAMPLES

Embodiments of the present invention will be more specifically describedwith reference to examples below. However, the present invention is notlimited to these examples. In the following syntheses and synthesisexamples, the structure of each compound was confirmed by ¹H-NMRmeasurement.

(Synthesis 1) Synthesis of CR-1A (Cyclic Compound (A))

Under a nitrogen gas stream, resorcinol manufactured by Kanto ChemicalCo., Inc. (22 g, 0.2 mol), 4-isopropylbenzaldehyde (29.6 g, 0.2 mol),and dehydrated ethanol (200 mL) were charged to a four necked flask(1000 mL) sufficiently dried, substituted with nitrogen, and equippedwith a dropping funnel, a Dimroth condenser tube, a thermometer, and astirring blade, to prepare an ethanol solution. The ethanol solution washeated to 85° C. by a mantle heater while stirring. Then, 75 mL ofconcentrated hydrochloric acid (35%) was dropped in the ethanol solutionthrough the dropping funnel for 30 minutes, and then continuouslystirred at 85° C. for 3 hours for reaction. After the reactionterminated, the obtained reaction liquid was stood to cool, and after itreached room temperature, it was cooled in an ice bath. The reactionliquid was left at rest for 1 hour, to produce a light yellow crudecrystal. The produced light yellow crude crystal was filtered, to obtaina crude crystal. The obtained crude crystal was washed twice with 500 mLmethanol, filtered, and dried in a vacuum to obtain 45.6 g of acompound. The result of LC-MS analysis showed that the compound had amolecular weight of 960 which was the same as that of an objectivecompound represented by the following formula (CR-1A). The chemicalshift value (δ ppm, TMS standard) of the obtained compound measured by¹H-NMR in a deuterated dimethyl sulfoxide solvent was 1.1 to 1.2 (m,24H), 2.6 to 2.7 (m, 4H), 5.5 (s, 4H), 6.0 to 6.8 (m, 24H), and 8.4 to8.5 (d, 8H). From these results, the obtained compound was identified asan objective compound (hereinafter, described also as “CR-1A”)represented by the following formula (CR-1A) (yield: 95%).

(Synthesis 2) Synthesis of CR-2A (Cyclic Compound (A))

In the same manner as in synthesis 1 except for using4-cyclohexylbenzaldehyde (46.0 g, 0.2 mol) in place of4-isopropylbenzaldehyde, 50 g of a compound was obtained. The result ofLC-MS analysis showed that the obtained compound had a molecular weightof 1121 which was the same as that of an objective compound representedby the following formula (CR-2A). The chemical shift value (5 ppm, TMSstandard) of the obtained compound measured by ¹H-NMR in a deuterateddimethyl sulfoxide solvent was 0.8 to 1.9 (m, 44H), 5.5 to 5.6 (d, 4H),6.0 to 6.8 (m, 24H), and 8.4 to 8.5 (m, 8H). From these results, theobtained compound was identified as an objective compound (hereinafter,described also as “CR-2A”) represented by the following formula (CR-2A)(yield: 91%).

Synthesis Example 1 Synthesis of CR-1 (Cyclic Compound)

In a four necked flask (1000 mL) sufficiently dried, substituted withnitrogen, and equipped with a dropping funnel, a Dimroth condenser tube,a thermometer, and a stirring blade, 3.6 g (40 mmol) of acryloylchloride was dropped to a solution of 9.6 g (10 mmol) of CR-1Asynthesized in synthesis 1 and 4 g (40 mmol) of triethylamine in 300 mLof THF cooled in an ice bath under a nitrogen gas stream. The resultantsolution was stirred at room temperature for 1 hour for reaction. Afterthe reaction terminated, the obtained reaction liquid was added to 1000ml of cold water, and the deposited solid was filtered. The obtainedsolid was purified by column chromatography, to obtain 10.6 g of acompound.

The chemical shift value (δ ppm, TMS standard) of the obtained compoundmeasured by ¹H-NMR in a deuterated dimethyl sulfoxide solvent was 1.1 to1.2 (m, 24H), 2.6 to 2.7 (m, 4H), 5.5 (m, 4H), 5.7 (m, 4H), 6.0 to 6.8(m, 32H), and 8.4 to 8.5 (m, 4H). From these results, the obtainedcompound was identified as a compound (hereinafter, described also as“CR-1”) in which 50 mol % of hydrogen atoms of phenolic hydroxyl groupsin CR-1A were substituted with acryloyl groups, and which wasrepresented by the following formula (CR-1).

(In CR-1, 50 mol % of R were acryloyl groups, and the remainder 50 mol %were hydrogen atoms.)

Synthesis Example 2 Synthesis of CR-2 (Cyclic Compound)

In the same manner as in synthesis example 1 except for using CR-2A(11.2 g, 10 mmol) in place of CR-1A, 11.2 g of a compound was obtained.The chemical shift value (δ ppm, TMS standard) of the obtained compoundmeasured by ¹H-NMR in a deuterated dimethyl sulfoxide solvent was 0.8 to1.9 (m, 44H), 5.5 to 5.6 (d, 4H), 5.7 (s, 4H), 6.0 to 6.8 (m, 32H), and8.4 to 8.5 (m, 4H). From these results, the obtained compound wasidentified as a compound (hereinafter, described also as “CR-2”) inwhich 50 mol % of hydrogen atoms of phenolic hydroxyl groups in CR-2Awere substituted with acryloyl groups, and which was represented by thefollowing formula (CR-2).

(In CR-2, 50 mol % of R were acryloyl groups, and the remainder 50 mol %were hydrogen atoms.)

Synthesis Example 3 Synthesis of CR-3 (Cyclic Compound)

In the same manner as in synthesis example 1 except for using 10.8 g(120 mmol) of acryloyl chloride in place of 3.6 g (40 mmol) of acryloylchloride, 11.0 g of a compound was obtained. The result of LC-MSanalysis showed that the obtained compound had a molecular weight of1393 which was the same as that of an objective compound represented bythe following formula (CR-3). The chemical shift value (δ ppm, TMSstandard) of the obtained compound measured by ¹H-NMR in a deuterateddimethyl sulfoxide solvent was 1.1 to 1.2 (m, 24H), 2.6 to 2.7 (m, 4H),5.5 (s, 4H), 5.7 (s, 8H), and 6.0 to 6.8 (m, 40H). From these results,the obtained compound was identified as a compound (hereinafter,described also as “CR-3”) in which 100 mol % of the hydrogen atoms ofthe phenolic hydroxyl groups in CR-1A were substituted with acryloylgroups, and which was represented by the following formula (CR-3).

Synthesis Example 4 Synthesis of CR-4 (Cyclic Compound)

In the same manner as in synthesis example 2 except for using 10.8 g(120 mmol) of acryloyl chloride in place of 3.6 g (40 mmol) of acryloylchloride, 11.4 g of a compound was obtained. The result of LC-MSanalysis showed that the obtained compound had a molecular weight of1553 which was the same as that of an objective compound represented bythe following formula (CR-4). The chemical shift value (δ ppm, TMSstandard) of the obtained compound measured by ¹H-NMR in a deuterateddimethyl sulfoxide solvent was 0.8 to 1.9 (m, 44H), 5.5 to 5.6 (d, 4H),5.7 (s, 8H), and 6.0 to 6.8 (m, 40H). From these results, the obtainedcompound was identified as a compound (hereinafter, described also as“CR-4”) in which 100 mol % of hydrogen atoms of phenolic hydroxyl groupsin CR-2A were substituted with acryloyl groups, and which wasrepresented by the following formula (CR-4).

Synthesis Example 5 Synthesis of CR-5 (Cyclic Compound)

In the same manner as in synthesis example 3 except for using 12.48 g(120 mmol) of methacryloyl chloride in place of 10.8 g (120 mmol) ofacryloyl chloride, 11.0 g of a compound was obtained. The result ofLC-MS analysis showed that the obtained compound had a molecular weightof 1521 which was the same as that of an objective compound representedby the following formula (CR-5). The chemical shift value (δ ppm, TMSstandard) of the obtained compound measured by ¹H-NMR in a deuterateddimethyl sulfoxide solvent was 1.1 to 1.2 (m, 24H), 1.9 (s, 12H), 2.6 to2.7 (m, 4H), 5.5 (s, 4H), 5.7 (s, 8H), and 6.0 to 6.8 (m, 32H). Fromthese results, the obtained compound was identified as a compound(hereinafter, described also as “CR-5”) in which 100 mol % of hydrogenatoms of phenolic hydroxyl groups in CR-1A were substituted withmethacryloyl groups, and which was represented by the following formula(CR-5).

Synthesis Example 6 Synthesis of CR-6 (Cyclic Compound)

In the same manner as in synthesis example 4 except for using 12.48 g(120 mmol) of methacryloyl chloride in place of 10.8 g (120 mmol) ofacryloyl chloride, 11.0 g of a compound was obtained. The result ofLC-MS analysis showed that the obtained compound had a molecular weightof 1681 which was the same as that of an objective compound representedby the following formula (CR-6). The chemical shift value (δ ppm, TMSstandard) of the obtained compound measured by ¹H-NMR in a deuterateddimethyl sulfoxide solvent was 0.8 to 1.9 (m, 44H), 2.0 (s, 24H), 5.5 to5.6 (d, 4H), 5.7 (s, 8H), and 6.0 to 6.8 (m, 32H). From these results,the obtained compound was identified as a compound (hereinafter,described also as “CR-6”) in which 100 mol % of hydrogen atoms ofphenolic hydroxyl groups in CR-2A were substituted with methacryloylgroups, and which was represented by the following formula (CR-6).

Examples 1 to 6 and Comparative Examples 1 to 2

Solubility Test of Compound in Safe Solvent

The dissolution amounts of compounds obtained in the above synthesisexamples 1 to 6 and syntheses 1 and 2 in propylene glycol monomethylether (PGME) and cyclohexanone (CHN) were evaluated as follows. Theevaluation result is shown in Table 1.

[Evaluation Criterion]

-   A: 5.0% by mass≦dissolution amount-   B: 3.0% by mass≦dissolution amount<5.0% by mass-   C: dissolution amount<3.0% by mass    *dissolution amount (% by mass)=mass (g) of compound dissolved in    100 g of solvent of 23° C./(100 g of mass of solvent+mass (g) of    compound dissolved in 100 g of solvent of 23° C.)×100

TABLE 1 Cyclic compound PGME CHN Example 1 CR-1 A B Example 2 CR-2 A AExample 3 CR-3 B A Example 4 CR-4 B A Example 5 CR-5 B A Example 6 CR-6B A Comparative CR-1A B C Example 1 Comparative CR-2A B B Example 2

From the results of the solubility test of the compounds in the safesolvent, it was found that examples 1 to 6 using the compounds of CR-1to 6 show better results of larger dissolution amounts in PGME and CHN,as compared to comparative examples 1 and 2 using CR-1A and CR-2A.

Examples 7 and 8 and Comparative Examples 3 and 4

(1) Preparation of Radiation-Sensitive Compositions

Components described in Table 2 were blended into homogeneous solutions,and then filtered through a membrane filter made of Teflon with a porediameter of 0.1 μm to prepare radiation-sensitive compositions.

TABLE 2 Acid Acid Acid diffusion Com- generating crosslinkingcontrolling pound agent (C) agent (G) agent (E) Solvent (g) (g) (g) (g)(g) Example 7 CR-3 P-1 C-1 Q-1 S-1 1.0 0.3 0.3 0.03 30.0 Example 8 CR-4P-1 C-1 Q-1 S-1 1.0 0.3 0.3 0.03 30.0 Comparative CR-1A P-1 C-1 Q-1 S-1Example 3 1.0 0.3 0.3 0.03 30.0 Comparative CR-2A P-1 C-1 Q-1 S-1Example 4 1.0 0.3 0.3 0.03 30.0 Acid Generating Agent (C) P-1:triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Kagaku Co.,Ltd.) Acid Crosslinking Agent (G) C-1: NIKALAC MW-100LM (Sanwa ChemicalCo., Ltd.) Acid Diffusion Controlling Agent (E) Q-1: trioctylamine(Tokyo Kasei Kogyo Co., Ltd.) Solvent S-1: propylene glycol monomethylether (Tokyo Kasei Kogyo Co., Ltd.)(2) Patterning Test

Patterning test was conducted as follows by using theradiation-sensitive composition prepared above.

A clean silicon wafer was spin coated with the radiation-sensitivecomposition prepared above, and then prebaked (PB) before exposure in anoven of 110° C. to form a resist film with a thickness of 60 nm. Theresist film was irradiated with electron beams of 1:1 line and spacesetting with a 50 nm interval, a 40 nm interval, and a 30 nm intervalusing an electron beam lithography system (ELS-7500 manufactured byELIONIX INC.). After irradiation, the resist films were heated at 110°C. for 90 seconds. The resist films formed from the radiation-sensitivecompositions prepared in examples 7 and 8 were immersed in a propyleneglycol-monomethyl ether acetate developing solution for 30 seconds fordevelopment. The resist films formed from the radiation-sensitivecompositions prepared in comparative examples 3 and 4 were immersed in a2.38% by mass TMAH aqueous solution for development. Subsequently, theresist films were washed with ultrapure water for 30 seconds, and driedto form negative type resist patterns.

The obtained resist patterns were observed by a scanning electronmicroscope (S-4800 manufactured by Hitachi High-TechnologiesCorporation). The minimum line width of the pattern which could beformed was used as the resolution of the pattern. The rectangularpattern shape was evaluated as goodness. For line edge roughness, theirregularity of the pattern of less than 5 nm was evaluated as goodness.A dose amount (μC/cm²) in this case was used as sensitivity. The doseamount of less than 150 μC/cm² was evaluated as goodness.

The result of the patterning test showed that, in theradiation-sensitive compositions of examples 7 and 8, a resist patternwith good resolution of 30 nm and high sensitivity could be obtained.The result of the patterning test showed that the roughness of thepattern was also small, and the shape was also good.

On the other hand, in the radiation-sensitive compositions ofcomparative examples 3 and 4, a resist pattern with good resolution of40 nm could be obtained, but, a resist pattern with good resolution of30 nm could not be obtained.

As described above, the composition containing the compound (forexample, CR-3 and CR-4) of the present embodiment was found to havehigher sensitivity, and enable the formation of the resist patternhaving a better shape having smaller roughness than that of thecomposition containing the corresponding comparative compound (forexample, CR-1A and CR-2A). As long as the requirements of the abovepresent embodiment are met, compounds other than those described inexamples also exhibit the same effects.

INDUSTRIAL APPLICABILITY

The present invention is preferably used in a cyclic compoundrepresented by a specific chemical constitution formula, which is usefulas an acid amplification type non-polymeric resist material, aradiation-sensitive composition containing the same, and a resistpattern formation method using the radiation-sensitive composition.

The invention claimed is:
 1. A cyclic compound having a molecular weight of 500 to 5000 and represented by formula (4):

wherein R¹ are each independently a hydrogen atom, a cyano group, a nitre group, a substituted or non-substituted heterocyclic group, a halogen atom, a substituted or non-substituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or non-substituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or non-substituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or non-substituted aryl group having 6 to 20 carbon atoms, a substituted or non-substituted alkylsilyl group having 1 to 20 carbon atoms, or a substituted or non-substituted alkenyl group having 2 to 20 carbon atoms; R⁴ are each independently a cyano group, a nitre group, a substituted or non-substituted heterocyclic group, a halogen atom, a substituted or non-substituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or non-substituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or non-substituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or non-substituted aryl group having 6 to 20 carbon atoms, a substituted or non-substituted alkoxy group having 1 to 20 carbon atoms, or a substituted or non-substituted alkylsilyl group having 1 to 20 carbon atoms; p is an integer of 0 to 5; and at least one of R¹ is a (meth)acryloyl group.
 2. The cyclic compound according to claim 1, wherein the cyclic compound represented by the formula (4) is represented by the formula (5):

wherein R⁴ are each independently a cyano group, a nitro group, a substituted or non-substituted heterocyclic group, a halogen atom, a substituted or non-substituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or non-substituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or non-substituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or non-substituted aryl group having 6 to 20 carbon atoms, a substituted or non-substituted alkoxy group having 1 to 20 carbon atoms, or a substituted or non-substituted alkylsilyl group having 1 to 20 carbon atoms; p is an integer of 0 to 5; and R⁵ is a (meth)acryloyl group.
 3. A method for producing the cyclic compound according to any one of claims 1 or 2, comprising the steps of: a condensation reaction of one or more aldehyde compounds (A1) with one or more phenolic compounds (A2) to obtain a cyclic compound (A); and a dehydrohalogenation reaction of the cyclic compound (A) with one or more (meth)acryloyl halides.
 4. The method for producing the cyclic compound according to claim 3, wherein: the aldehyde compound (A1) has 1 to 4 formyl groups and has 1 to 59 carbon atoms; and the phenolic compound (A2) has 1 to 3 phenolic hydroxyl groups and has 6 to 15 carbon atoms.
 5. A radiation-sensitive composition comprising a solid component containing the cyclic compound according to claim 1 and a solvent.
 6. The radiation-sensitive composition according to claim 5, comprising 1 to 80% by weight of the solid component.
 7. The radiation-sensitive composition according to claim 5, wherein a content of the cyclic compound is 50 to 99.999% by weight based on a total weight of the solid component.
 8. The radiation-sensitive composition according to claim 5, further comprising an acid generating agent (C) which directly or indirectly generates acid upon exposure to any radiation selected from the group consisting of visible light, ultraviolet, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam.
 9. The radiation-sensitive composition according to claim 5, further comprising an acid crosslinking agent (G).
 10. The radiation-sensitive composition according to claim 5, further comprising an acid diffusion controlling agent (E).
 11. The radiation-sensitive composition according to claim 5, wherein the solid component comprises 50 to 99.4% by weight of the cyclic compound, 0.001 to 49% by weight of an acid generating agent (C), 0.5 to 49% by weight of an acid crosslinking agent (G), and 0.001 to 49% by weight of an acid diffusion controlling agent (E).
 12. The radiation-sensitive composition according to claim 5, forming an amorphous film by spin coating.
 13. The radiation-sensitive composition according to claim 12, wherein a dissolution rate of the amorphous film into a developing solution at 23° C. is 10 angstrom/sec or more.
 14. The radiation-sensitive composition according to claim 12, wherein a dissolution rate of the amorphous film into a developing solution is 5 angstrom/sec or less after exposed to KrF excimer laser, extreme ultraviolet, electron beam, or X-ray, or after heated at 20 to 250° C.
 15. A method for forming a resist pattern, comprising the steps of: forming a resist film by coating a substrate with the radiation-sensitive composition according to claim 5; exposing the resist film; and developing the exposed resist film. 